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WO2015115330A1 - Transistor en couches minces, semi-conducteur à base d'oxyde et son procédé de production - Google Patents

Transistor en couches minces, semi-conducteur à base d'oxyde et son procédé de production Download PDF

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Publication number
WO2015115330A1
WO2015115330A1 PCT/JP2015/051845 JP2015051845W WO2015115330A1 WO 2015115330 A1 WO2015115330 A1 WO 2015115330A1 JP 2015051845 W JP2015051845 W JP 2015051845W WO 2015115330 A1 WO2015115330 A1 WO 2015115330A1
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Prior art keywords
oxide
semiconductor layer
film transistor
thin film
semiconductor
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English (en)
Japanese (ja)
Inventor
一仁 塚越
慎也 相川
たきお 木津
麻希 清水
伸彦 三苫
生田目　俊秀
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National Institute for Materials Science
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National Institute for Materials Science
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Priority claimed from JP2014016273A external-priority patent/JP6252903B2/ja
Priority claimed from JP2014016631A external-priority patent/JP6252904B2/ja
Priority claimed from JP2014016630A external-priority patent/JP6261125B2/ja
Application filed by National Institute for Materials Science filed Critical National Institute for Materials Science
Publication of WO2015115330A1 publication Critical patent/WO2015115330A1/fr
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    • H10P14/22—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
    • H10D30/6756—Amorphous oxide semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D99/00—Subject matter not provided for in other groups of this subclass
    • H10P14/3426—
    • H10P14/3434—

Definitions

  • the first to third inventions of the present application relate to an oxide thin film transistor and a method for manufacturing the same.
  • the fourth invention of the present application also relates to a thin film transistor and a method for manufacturing the same.
  • the fifth invention of the present application relates to an oxide semiconductor, a manufacturing method thereof, a thin film transistor using the same, and a semiconductor device.
  • TFTs Thin film transistors
  • EL organic electroluminescence
  • the TFT As the TFT, a semiconductor layer (channel layer) using amorphous silicon or polysilicon is known. In recent years, in order to improve various characteristics, the semiconductor layer has an In (indium) -Zn (zinc) -O (IZO) system, an In-Ga (gallium) -Zn-O (IGZO) system, or Sn (tin).
  • IZO In (indium) -Zn (zinc) -O
  • IGZO In-Ga (gallium) -Zn-O
  • Sn Tin
  • Such a thin film transistor has n-type conductivity and exhibits higher channel mobility than amorphous silicon or polysilicon, it can be suitably used as a switching element for a high-definition display or a large-screen display.
  • oxygen vacancies are mainly introduced by desorption of oxygen to the indium oxide structure, and as a result, charge is generated to serve as a semiconductor layer.
  • a semiconductor layer made of a metal oxide does not exhibit p-type conduction in principle and has a very small off current, the use of a thin film transistor has an advantage that power consumption can be reduced.
  • the thin film transistor is preferably used as a switching element of a liquid crystal display or an organic electroluminescence display as described above, a relatively high-intensity visible light is irradiated in its use.
  • characteristics of relatively short wavelength (high energy) components for example, light irradiation with a wavelength of 420 nm (2.95 eV) may deteriorate characteristics such as a shift in threshold voltage of a thin film transistor.
  • it is desirable that the contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer is low, that the electron mobility is high, and that the gate controllability is excellent, and that these characteristics are also excellent. It has been.
  • the IZO, IGZO, and SZO metal oxides which are metal oxides described in Patent Document 1, can easily react with the water in the Zn, Ga, and Sn contained therein. As a physical structure, unstable suboxide is formed, and the amount of oxygen vacancies cannot be adjusted, resulting in a problem of greatly degrading transistor characteristics.
  • Patent Document 7 discloses, as a metal oxide, a material containing at least one element of zinc and tin, yttrium, niobium, tantalum, hafnium, lanthanum, scandium, vanadium, titanium, magnesium. It is disclosed that at least one of aluminum, gallium and silicon is used. In addition, in order to suppress fluctuations in threshold voltage caused by the destruction effect due to plasma damage and the increase in carriers due to radiation effects in the thin film transistor manufacturing stage, at least one of gallium, indium, tin, zirconium, hafnium, and vanadium is added to zinc oxide. It is disclosed to dope one ion (Patent Document 8).
  • Non-Patent Document 1 electrical characteristics of an oxide film transistor of an IZO metal oxide doped with tantalum have been reported.
  • Non-Patent Document 1 since zinc is contained as a main element, there is a serious problem that a considerable limitation is imposed on the process in order to suppress the formation of suboxides in the thin film transistor manufacturing stage.
  • Patent Document 2 there is a report that indium oxide doped with either tin, titanium, or tungsten is used instead of IZO or IGZO as a metal oxide.
  • Patent Document 2 the oxide film transistor using indium oxide doped with either titanium or tungsten described in the above document as the metal oxide, the amount of oxygen vacancies introduced into the main structure indium oxide is adjusted at the metal oxide production stage. There is a big problem that the manufacturing process is limited because it is very difficult to do.
  • the inventors of the present invention have described that the oxygen separation energy of the metal (Me) -O bond or nonmetal-O bond to the first metal oxide such as indium oxide is 200 kJ / mol than the oxygen separation energy of the first metal oxide.
  • a thin film transistor in which the amount of oxygen vacancies in the above problem was controlled by adding a large oxide as described above and a method for manufacturing the same were filed (Japanese Patent Application No. 2013-099284).
  • Japanese Patent Application No. 2013-099284 Japanese Patent Application No. 2013-099284
  • a semiconductor layer (channel layer) using amorphous silicon or polysilicon used for a TFT is known.
  • various metals are used for a semiconductor layer in order to improve various characteristics.
  • a TFT using an oxide has been studied (for example, see Patent Document 1).
  • Patent Document 9 discloses a semiconductor device including a transistor in which a source electrode layer and a drain electrode layer are provided in contact with an oxide semiconductor film.
  • Patent Document 10 in a method for manufacturing a semiconductor device using an oxide semiconductor, an oxide semiconductor film, a gate insulating film provided over the oxide semiconductor film, a gate electrode in contact with the gate insulating film, and a gate A step of forming a sidewall insulating film in contact with the electrode and a source electrode and a drain electrode in contact with the oxide semiconductor film, and the gate insulating film and the sidewall insulating film release oxygen contained in the oxide semiconductor film.
  • a method of forming at a temperature lower than the temperature at which separation is suppressed is disclosed.
  • Patent Document 11 discloses a gate electrode on an insulating substrate, a gate insulating film on the gate electrode, an oxide semiconductor film containing indium on the gate insulating film, and a source / drain on the oxide semiconductor film.
  • the XPS spectrum in the oxide semiconductor region where the peak position due to the indium 3d orbit of the XPS spectrum in the surface layer of the oxide semiconductor film where the source / drain electrodes do not overlap is present in the lower part of the surface layer.
  • a TFT that is shifted to a higher energy side than the peak position due to the indium 3d orbital is disclosed.
  • the first to third inventions of the present application have been made in view of such circumstances, and the first metal oxide capable of generating electron carriers by introducing oxygen vacancies into the semiconductor layer (channel layer), A thin film transistor using a composite metal oxide to which a second oxide having a larger oxygen dissociation energy than that of the first metal oxide is added at least 200 kJ / mol and having a specific element distribution.
  • An object of the present invention is to provide a thin film transistor and a method for manufacturing the same, which are compatible with suppression of characteristic deterioration due to light irradiation, low contact resistance, and excellent gate controllability.
  • the subject of the 4th invention of this application is providing the thin-film transistor which solves the said problem on composition conditions other than having shown by the prior patent application mentioned above, and its manufacturing method.
  • a light emitting layer is used for an organic EL display or a liquid crystal display.
  • light emission from the blue light emitting layer having the highest energy that is, light emitted at a short wavelength has a peak at 450 nm, and the bottom of the emission spectrum extends to 420 nm on the short wavelength side.
  • the thin film transistors constituting the organic EL display and the liquid crystal display are irradiated with light from the light emitting layer, it is desired that the thin film transistor be highly resistant to deterioration with respect to light irradiation having the above wavelength. It is rare. Here, it is difficult to deteriorate against light irradiation from the light emitting layer.
  • the oxide semiconductor constituting the thin film transistor emits light from the light emitting layer (specifically, a wavelength of 420 nm to 600 nm).
  • “Threshold voltage shift” induced by light irradiation (where “threshold voltage shift” refers to a phenomenon in which the threshold voltage shifts to the negative side due to light emission from the light emitting layer). .) Can be suppressed. Therefore, in order to provide a highly reliable thin film transistor, an oxide semiconductor that can sufficiently suppress this “threshold voltage shift” is desired.
  • any of the oxide semiconductor films disclosed in the above-mentioned patent documents has a problem that the “threshold voltage shift” induced by light emission from the light emitting layer cannot be sufficiently suppressed.
  • an oxide semiconductor used for a thin film transistor constituting an organic EL display or a liquid crystal display is desired to be able to sufficiently suppress a “threshold voltage shift” induced by light emission from a light emitting layer.
  • the fifth invention of the present application was made in view of such circumstances, and an oxide semiconductor capable of sufficiently suppressing a “threshold voltage shift” induced by light emission from the light emitting layer, a manufacturing method thereof, and It is an object to provide a thin film transistor and a semiconductor device using the thin film transistor.
  • the semiconductor device in this specification includes all devices using a transistor made of a semiconductor. Therefore, for example, an organic EL display and a liquid crystal display are also included in this.
  • the present inventor has at least one element X selected from the group consisting of silicon, tantalum, zirconium, hafnium, aluminum, yttrium and rare earth elements among the elements X constituting the second oxide (XOx). It has been found that a thin film transistor in which the concentration of 1 exhibits a maximum value in the central portion in the thickness direction of the semiconductor layer solves the above problems, and has led to the first to third inventions of the present application.
  • the first invention of the present application is [1] a source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the concentration of at least one element X 1 selected from the group consisting of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements is in the thickness direction of the semiconductor layer.
  • the present invention relates to the above-described thin film transistor, which exhibits a maximum value at the center.
  • the concentration of the element X 1 shows a maximum value in the central portion in the thickness direction of the semiconductor layer.
  • the second invention of the present application is [3] a source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the concentration of at least one element X 2 that does not correspond to any of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements is in the thickness direction of the semiconductor layer.
  • the present invention relates to the above-described thin film transistor that exhibits a minimum value in the center.
  • the following [4] is a preferred embodiment of the second invention of the present application [4]
  • the concentration of the element X 2 shows a minimum value in the central portion in the thickness direction of the semiconductor layer.
  • the third invention of the present application is [5] a source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the said thin film transistor is related with the said thin-film transistor in which the said semiconductor layer contains nitrogen further, and the density
  • [6] to [17] are preferred embodiments of the first to third inventions of the present application [6].
  • Zr zirconium
  • Pr praseodymium
  • the thin film transistor according to any one of [1] to [12], wherein the thickness of the semiconductor layer is in the range of 5 nm to 20 nm.
  • the semiconductor layer is formed at a temperature of 10 ° C. or higher and 400 ° C. or lower; The method for producing a thin film transistor according to any one of [1] to [15] above.
  • [17] The method for producing a thin film transistor according to [16], wherein the semiconductor layer is formed at a temperature of 10 ° C. or higher and 200 ° C. or lower.
  • the apparatus which has a thin-film transistor of any one of said [1] to [15].
  • a source electrode and a drain electrode, a semiconductor layer provided in contact with the source electrode and the drain electrode, and a channel between the source electrode and the drain electrode are supported. And an insulating layer provided between the gate electrode and the semiconductor layer.
  • the semiconductor layer has tin oxide, an oxygen separation energy larger than that of tin oxide, and an oxide layer.
  • a thin film transistor which is a composite metal oxide to which a metal oxide having a difference from the separation energy of oxygen of tin of less than 200 kJ / mol is added is provided.
  • the semiconductor layer may include an additional oxide whose oxygen dissociation energy is smaller than that of tin oxide in an amount smaller than that of the metal oxide.
  • the content of the additional oxide in the semiconductor layer may be 20% by weight or less.
  • the content of the additional oxide in the semiconductor layer may be 4% by weight or less.
  • the semiconductor layer may be amorphous.
  • the semiconductor layer may have a thickness of 5 nm to 20 nm.
  • the additional oxide may be at least one oxide selected from the group consisting of lead, palladium, platinum, sulfur, antimony, strontium, thallium, and ytterbium.
  • the metal oxide may be at least one oxide selected from the group consisting of samarium, tungsten, neodymium, and gadolinium.
  • the content of the metal oxide in the semiconductor layer may be greater than 0 and 50% by weight or less. [29] Further, the content of the metal oxide in the semiconductor layer may be 5% by weight or less. [30] According to another aspect of the fourth invention of the present application, there is provided a method for producing any one of the above thin film transistors, wherein the semiconductor layer is formed at 10 ° C. or more and 500 ° C. or less. [31] Here, you may form the said semiconductor layer at 10 degreeC or more and 300 degrees C or less.
  • the present inventor has found that the first metal oxide made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies and the oxygen separation energy are the first.
  • An oxide semiconductor into which oxygen vacancies are introduced is formed, which includes a second oxide that is 200 kJ / mol or more larger than the oxygen separation energy of one metal oxide, and further has OH as a substituent in the oxygen vacancies.
  • the oxide semiconductor in which at least one selected from the group consisting of a group, an H group, an F group, a Cl group, or a B group is introduced and bonded to the metal of the first metal oxide is used as a thin film transistor, It has been found for the first time that the “threshold voltage shift” induced by light emission from the light emitting layer can be sufficiently suppressed.
  • the fifth invention of the present application has a configuration shown in the following [32] to [57].
  • a first metal oxide made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and an oxygen separation energy of 200 kJ / mol or more than the oxygen separation energy of the first metal oxide.
  • An oxide semiconductor comprising a large second oxide, wherein the metal of the first metal oxide is at least selected from the group consisting of an OH group, an H group, an F group, a Cl group, or a B group The oxide semiconductor having a bond with one.
  • the oxide semiconductor according to [32] wherein the oxygen separation energy of the second oxide is greater than or equal to 255 kJ / mol than the oxygen separation energy of the first metal oxide.
  • the second oxide includes silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), lanthanum (La), hafnium (Hf), zirconium (Zr), and praseodymium (Pr).
  • the second oxide is at least one selected from the group consisting of silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), lanthanum (La), and hafnium (Hf).
  • the oxide semiconductor according to [35] The oxide semiconductor according to [35].
  • [37] The oxide semiconductor according to any one of [32] to [36], wherein the content of the second oxide is greater than 0 and equal to or less than 50% by weight.
  • [38] The oxide semiconductor according to [37], wherein the content of the second oxide is greater than 0 and 5% by weight or less.
  • the content of at least one selected from the group consisting of the F group, the Cl group, or the B group is more than 5 ⁇ 10 18 atoms / cm 3 and not more than 1 ⁇ 10 21 atoms / cm 3
  • a thin film transistor comprising the oxide semiconductor according to any one of [32] to [49].
  • a source electrode and a drain electrode A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; Providing an insulator layer provided between the gate electrode and the semiconductor layer; A thin film transistor, wherein the semiconductor layer is formed of the oxide semiconductor according to any one of [32] to [49].
  • a semiconductor device comprising the thin film transistor according to [51].
  • the first metal oxide powder made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and the oxygen separation energy of the first metal oxide is 200 kJ / day higher than the oxygen separation energy of the first metal oxide.
  • the first metal oxide powder made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and the oxygen separation energy of the first metal oxide is 200 kJ / day higher than the oxygen separation energy of the first metal oxide.
  • the first metal oxide powder made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and the oxygen separation energy of the first metal oxide is 200 kJ / day higher than the oxygen separation energy of the first metal oxide.
  • characteristic deterioration such as threshold current shift due to light irradiation is suppressed, contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer is low, and electron transfer is suppressed.
  • a thin film transistor having a high level of practically preferable characteristics of high degree and excellent gate controllability, and a method for manufacturing the same are realized.
  • the metal oxide added thereto is in addition, the composite metal oxidation in which the oxygen separation energy of the added metal oxide is larger than the oxygen separation energy of tin oxide and the difference from the oxygen separation energy of tin oxide is less than 200 kJ / mol.
  • a thin film transistor with excellent transistor characteristics can be provided by using a semiconductor layer.
  • an oxide having an oxygen separation energy smaller than that of tin oxide is added in an amount smaller than that of the metal oxide to be added.
  • the fifth invention of the present application it is possible to provide an oxide semiconductor capable of sufficiently suppressing “threshold voltage shift” induced by light emission from the light emitting layer. Therefore, a thin film transistor using the oxide semiconductor, an organic EL display using the thin film transistor, and a liquid crystal display can have high reliability that the light emission from the light emitting layer hardly deteriorates.
  • Patent Document 9 discloses that the above oxide processed into an island shape in a semiconductor device having a transistor in which a source electrode layer and a drain electrode layer are provided in contact with an oxide semiconductor film such as an IZO or IGZO system.
  • concentration of fluorine, chlorine, and boron in a region not overlapping with the source electrode layer and the drain electrode layer on the side surface portion of the semiconductor film is disclosed.
  • this fluorine, chlorine, and boron are impurities contained in the etching gas, and must be removed as much as possible by the impurity removal treatment by solution cleaning in order to prevent the formation of parasitic channels due to their contamination. (See paragraphs 0184 and 0185, for example).
  • Patent Document 10 discloses that in a method for manufacturing a semiconductor device using an oxide semiconductor, one or more elements selected from boron, a rare gas element, and the like are used as a dopant.
  • this patent document does not describe the amount of dopant.
  • this dopant is implanted only to reduce the resistance of the oxide semiconductor in contact with the source electrode and the drain electrode, the amount of this dopant is very small, 5 ⁇ 10 18 atoms. / Cm 3 is presumed not to exceed. Therefore, even in Patent Document 10, it is not recognized that the metal constituting the oxide semiconductor film is bonded to such an extremely low concentration of boron or a rare gas element.
  • a region of the oxide semiconductor film located in a portion masked with the gate electrode contains boron or a rare gas element.
  • a metal that forms the oxide semiconductor film is boron used as a dopant. It does not combine with noble gas elements. Due to such differences, the oxide semiconductor film described in Patent Document 10 cannot obtain the above-described effect of the fifth invention of the present application.
  • Patent Document 11 a surface layer is formed as a separate layer different from the oxide semiconductor film in a portion where the source / drain electrodes of the oxide semiconductor film do not overlap with each other, and chemicals of indium and fluorine are formed only on the surface layer.
  • a TFT providing a bond is disclosed.
  • the TFT described in Patent Document 11 does not introduce fluorine into the oxide semiconductor film existing under the surface layer as a separate layer different from the surface layer.
  • a region mainly on the gate electrode side of the oxide semiconductor film functions as a channel region.
  • the dopant exists in at least the interface region with the gate electrode in the oxide semiconductor film (of course, the dopant may also exist in other regions). Therefore, in the oxide semiconductor film described in Patent Document 11, the above effect according to the fifth invention of the present application cannot be obtained.
  • FIG. 1 is a schematic cross-sectional view of a thin film transistor according to an embodiment of the first invention of the present application.
  • 1 is a schematic cross-sectional view of a thin film transistor according to an embodiment of the first invention of the present application.
  • FIG. 6 shows a relationship between the composition of an In—Si—O film and a band gap.
  • the figure which shows the X-ray-diffraction pattern for confirming that the semiconductor film used by 2nd Example (Example B2) of this invention 4th invention is amorphous.
  • the figure which shows the Id-Vd characteristic of the thin-film transistor of 2nd Example (Example B2) of this-application 4th invention is amorphous.
  • In-Si-O semiconductor of Example C and In-Si-O semiconductor having In-OH bond ((a) In3dXPS spectrum of In-Si-O semiconductor, (b) In-Si having In-OH bond) -In3dXPS spectrum of -O semiconductor).
  • the thin film transistor of the first invention of this application is: A source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the concentration of at least one element X 1 selected from the group consisting of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements is in the thickness direction of the semiconductor layer.
  • the thin film transistor having a maximum value in the center.
  • the concentration of the specific element X 1 is in the thickness direction of the semiconductor layer is continuously and substantially change, that is, the element X 1 is a concentration gradient in the thickness direction of the semiconductor layer ing. More specifically, the concentration of the element X 1 shows a maximum value, that is, at least one peak in the central portion in the thickness direction of the semiconductor layer.
  • the “central portion” refers to both the interfaces of the semiconductor layer (usually, the interface in contact with the interlayer insulating film on the source electrode and drain electrode side and the interface in contact with the insulator layer on the gate electrode side). It refers to a location 2 nm or more, or 5% or more of the thickness of the semiconductor layer.
  • the at least one concentration of the element X 1 represents the maximum value in the central portion in the thickness direction of the semiconductor layer. That is, the concentration of the element X 1 in any location of the central portion in the thickness direction of the semiconductor layer is preferably higher than the concentration of the element X 1 in any position of the semiconductor layer.
  • the concentration of the element X 1 is, by indicating a maximum value in the central portion in the thickness direction of the semiconductor layer, characteristic deterioration such as a shift in the threshold current due to light irradiation can be suppressed, the source electrode And / or a remarkable technical effect that the contact resistance at the interface between the drain electrode and the semiconductor layer is low, the electron mobility is high, and the gate controllability is excellent is realized.
  • the thin film transistor of the first invention of the present application is preferably manufactured by a manufacturing method including a step of forming a semiconductor layer at 10 ° C. or higher and 400 ° C. or lower.
  • FIG. 1 is a schematic cross-sectional view of a thin film transistor 10 according to a preferred embodiment of the first invention of the present application.
  • the substrate 20 a substrate formed of a known forming material can be used, and any of those having optical transparency and those having no optical transparency can be used.
  • an inorganic substrate made of alkali silicate glass, quartz glass, silicon nitride, or the like; a silicon substrate; a metal substrate whose surface is insulated; acrylic resin, polycarbonate resin, PET (polyethylene terephthalate), or PBT (polybutylene)
  • Various substrates such as a resin substrate made of a polyester resin such as terephthalate) or a paper substrate can be used.
  • the substrate may be a composite material formed by combining a plurality of these materials.
  • the thickness of the substrate 20 can be appropriately set according to the design.
  • the thin film transistor 10 of this embodiment is a so-called bottom gate type transistor.
  • the thin film transistor 10 includes a gate electrode 30 provided on the substrate 20, an insulator layer 40 provided to cover the gate electrode 30, a semiconductor layer 50 provided on the upper surface of the insulator layer 40, A source electrode 60 and a drain electrode 70 provided in contact with the semiconductor layer 50 on the upper surface, and an interlayer insulating film 80 are provided.
  • the gate electrode 30 is provided corresponding to the channel region of the semiconductor layer 50 (at a position overlapping the channel region in a plan view).
  • the semiconductor layer 50 is composed of a composite metal oxide obtained by adding a second oxide (XOx) to a first metal oxide capable of generating electron carriers by introducing oxygen vacancies.
  • the semiconductor layer may contain components other than the second oxide and inevitable impurities as long as the adverse effects of the first invention of the present application are not adversely affected.
  • Each of the gate electrode 30, the source electrode 60, and the drain electrode 70 can be made of a generally known material.
  • the material for forming these electrodes include aluminum (Al), gold (Au), silver (Ag), copper (Cu), nickel (Ni), molybdenum (Mo), tantalum (Ta), and tungsten (W).
  • Examples thereof include metal materials such as these, alloys thereof, and conductive oxides such as indium tin oxide (ITO) and zinc oxide (ZnO).
  • these electrodes may form the laminated structure of two or more layers, for example by plating the surface with a metal material.
  • the gate electrode 30, the source electrode 60, and the drain electrode 70 may be formed of the same forming material or may be formed of different forming materials. Since manufacture becomes easy, it is preferable that the source electrode 60 and the drain electrode 70 are the same formation material.
  • the insulator layer 40 has an insulating property, and any of an inorganic material and an organic material can be used as long as it can electrically insulate the gate electrode 30 from the source electrode 60 and the drain electrode 70. It may be formed.
  • the inorganic material include normally known insulating oxides such as SiO 2 , SiN x , SiON, Al 2 O 3 , and HfO 2 , nitrides, and oxynitrides.
  • the organic material include acrylic resin, epoxy resin, silicon resin, and fluorine resin.
  • the organic material is preferably a photocurable resin material because it is easy to manufacture and process.
  • the semiconductor layer 50 includes a second metal oxide having energy greater than that of the first metal oxide that can generate electron carriers by introducing oxygen vacancies by 200 kJ / mol or more. It is formed of a complex oxide containing an oxide.
  • the first metal oxide is preferably a metal oxide including at least one selected from the group consisting of indium (In), gallium (Ga), zinc (Zn), and tin (Sn), and the second The oxide is preferably zirconium (Zr), silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), hafnium (Hf), scandium (Sc), yttrium (Y), lanthanum (La).
  • the element of the first oxide is In
  • the element of the second oxide is at least selected from the group consisting of Zr, Pr, Si, Ti, W, Ta, La, Hf, B, and C.
  • the element of the second oxide is at least one element selected from the group consisting of Sc, Ti, W, Nd, and Gd.
  • the oxygen separation energy of indium oxide is as small as 346 ⁇ 30 kJ / mol, so oxygen is easily desorbed from indium oxide to generate oxygen vacancies. It's easy to do. However, if the amount of oxygen vacancies becomes too large, it changes from semiconducting properties to metallic properties, making it unsuitable as a semiconductor layer.
  • a second oxide (XO x ) having an oxygen separation energy of 200 kJ / mol / greater than the oxygen separation energy of indium oxide more specifically,
  • the second metal oxide which is a metal oxide, or an equivalent nonmetallic element oxide as described later may be added.
  • the oxygen separation energy of the second oxide is preferably larger than that specified above, and an oxide having an oxygen separation energy of 725 kJ / mol or more, more preferably 780 kJ / mol or more is used as the second oxide. When used, it is preferable because the oxygen deficiency of indium oxide can be easily controlled.
  • the oxygen separation energy of the second oxide is 200 kJ / mol or more as compared with the first metal oxide.
  • a thing larger than 255 kJ / mol may be used.
  • a metal oxide is preferably used as the second oxide, but as a particularly suitable metal oxide, Table A1 in which oxides having an oxygen separation energy of 780 kJ / mol or more are summarized and oxygen As shown in Table A2, which summarizes metal oxides having a separation energy of 725 kJ / mol to 780 kJ / mol, zirconium oxide (Zr—O), praseodymium oxide (Pr—O), lanthanum oxide (La—O), Examples include, but are not limited to, tantalum oxide (Ta—O) and hafnium oxide (Hf—O). Similarly, silicon oxide (Si—O) described in Table A1 is also preferable as the second oxide.
  • the second oxide added to make the first metal oxide a semiconductor layer having an appropriate oxygen deficiency is particularly preferably a second oxide of 780 kJ / mol or more shown in Table A1. Is more preferable. Specifically, lanthanum oxide (La—O), silicon oxide (Si—O), tantalum oxide (Ta—O), and hafnium oxide (Hf—O) can be given.
  • the content of the second oxide added to the first metal oxide in order to make the first metal oxide a semiconductor layer having a suitable oxygen deficiency is not particularly limited, but is larger than 0 and 50% by weight. The following range is recommended. In particular, when the content of the second oxide added to the first metal oxide is in the range of more than 0 and 5% by weight or less, it is practically preferable in that it can be produced at a low temperature of 200 ° C. or less.
  • In-Zn-O-based and In-Ga-Zn-O-based metal oxides tend to be polycrystalline when a semiconductor layer is formed. Therefore, in a generally known thin film transistor, the surface of the semiconductor layer does not become flat due to crystal grains contained in the semiconductor layer. In addition, the normally known semiconductor layer of an oxide film transistor has a reduced electrical conductivity in the plane direction due to such crystal grains. Therefore, in order to obtain planarization of the surface of the semiconductor layer 50 and high electrical conductivity, the semiconductor layer preferably has an amorphous structure.
  • the thickness of the semiconductor layer 50 is not particularly limited, but is preferably in the range of 5 nm or more and 20 nm or less.
  • the thickness of the semiconductor layer 50 can be measured by using a crystal oscillation type film thickness meter arranged mainly for film thickness calibration in the sputtering chamber in which the semiconductor layer 5 is formed. .
  • the composite metal oxide which comprises the semiconductor layer 50 is not limited to what added the metal oxide as a 2nd oxide to the 1st metal oxide, and the separation energy is 200 kJ / in comparison with the 1st metal oxide.
  • a non-metal oxide larger than mol may be added.
  • the composite metal oxide may be, for example, an oxide of at least one element selected from boron (B) and carbon (C) (ie, “composite metal oxide” in the present application). Is used to mean "an oxide in which a metal oxide is combined with an element having an energy greater than a predetermined value for oxygen").
  • the oxygen desorption energy of the B—O bond is as large as 809 kJ / mol and the oxygen desorption energy of the C—O bond is as large as 1076.38 ⁇ 0.67 kJ / mol, so that the amount of oxygen deficiency introduced into the first metal oxide This is because it can be easily controlled.
  • the concentration of the element X 1 is selected from the group consisting of yttrium and rare earth elements, semiconductor
  • the maximum value is shown at the center in the thickness direction of the layer.
  • oxygen in the vicinity of the valence band of the In 2 O 3 band gap is caused by light absorption as a factor of the threshold voltage shift of the thin film transistor due to light irradiation with a wavelength of 420 nm. It is estimated that electrons hop from a level due to defects to a trap level near the conduction band.
  • the band gap of In 2 O 3 is about 3.7 eV, and the above-mentioned electron hopping is achieved by enlarging the conduction band of this band gap (from the vacuum level to 4.05 eV) (closer to the vacuum level side). It can be expected that the energy required for the above can be increased, and as a result, the shift of the threshold voltage due to light irradiation can be suppressed.
  • FIG. 3 shows the evaluation results of the band gap by photoelectron yield spectroscopy of an In—Si—O film having a thickness of 50 nm with SiO 2 weights of 1, 3 and 10% by weight, respectively.
  • the band gap which was about 3.7 eV when the SiO 2 content was 1% by weight, could be increased to 4.5 eV by increasing the SiO 2 content to 10% by weight.
  • candidate oxides that can have the effect of expanding the band gap like SiO 2 are Ta 2 O 5 (+0.3 eV), ZrO 2 (+1.4 eV), HfO. 2 (+1.5 eV), Al 2 O 3 (+2.8 eV), Y 2 O 3 (+1.3 eV) and rare earth oxides. Therefore, among the elements X constituting the first oxide XO x , the element X 1 added for the purpose of suppressing the threshold voltage shift is silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements.
  • Si 3 N 4 (+2.4 eV) can also have an effect of widening the band gap, and Si 3 N 4 can be used as a semiconductor together with or in place of the second oxide. It is also preferable to add to the composite metal oxide constituting the layer.
  • the concentration of the oxide of the element X 1 introduced into the In 2 O 3 film is usually 3% by weight or more and 50% by weight or less. Particularly, the concentration range of 10 to 30% by weight suppresses undesirable effects due to the addition. This is preferable from the viewpoint of expanding the gap.
  • the element X 1 of the semiconductor layer is a semiconductor layer, a high density at the central portion, having a concentration gradient of a low density at both interfaces. That is, the at least one concentration of the element X 1 represents a local maximum value, i.e. at least one peak at the center in the thickness direction of the semiconductor layer.
  • the meaning of the “central part” is as described above.
  • the concentration of oxide of the element X 1 is the maximum value in the central portion in the thickness direction of the semiconductor layer, for example, 3 wt% or more, 50 wt% or less, preferably 10 wt% As described above, it is preferably 30% by weight or less, and preferably has a concentration gradient that decreases monotonously as it approaches both interfaces.
  • the concentration of the oxide of the element X 1 at both interfaces is not particularly limited as long as it is substantially lower than the concentration at the center, and is preferably 0.1% by weight or less, for example, substantially zero. It is particularly preferred that
  • the concentration of the element X 1 in both interfaces is low, the contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer is low and excellent in high gate controllability electron mobility That is, a practically preferable characteristic can be realized.
  • concentration of the element X 1 in the composite oxide constituting the semiconductor layer at the interface between the source electrode and / or drain electrode and the semiconductor layer is low, the composite oxide will have a tendency to release oxygen .
  • the complex oxide in the vicinity of the interface with the source electrode and / or drain electrode generates oxygen vacancies and is so-called metalized, and the contact resistance with the source electrode and / or drain electrode is reduced.
  • the thin film transistor of the second invention of the present application A source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the concentration of at least one element X 2 that does not correspond to any of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements is in the thickness direction of the semiconductor layer.
  • the thin film transistor having a minimum value in the center.
  • the concentration of the at least one element X 2 continuously and substantially varies in the thickness direction of the semiconductor layer, that is, the at least one element X 2 is in the thickness direction of the semiconductor layer. It has a concentration gradient. More specifically, the concentration of the at least one element X 2 has a minimum value at the center in the thickness direction of the semiconductor layer.
  • the “central portion” refers to both the interfaces of the semiconductor layer (usually, the interface in contact with the interlayer insulating film on the source electrode and drain electrode side and the interface in contact with the insulator layer on the gate electrode side). It refers to a location 2 nm or more, or 5% or more of the thickness of the semiconductor layer.
  • the at least one element X 2 concentration shows a minimum value at the central portion in the thickness direction of the semiconductor layer. That is, the concentration of the element X 2 in any location of the central portion in the thickness direction of the semiconductor layer is preferably lower than the concentration of the element X 2 in any other portion of the semiconductor layer.
  • the at least one element X 2 is an element constituting the second oxide, that is, an element constituting the second oxide (XO x ) that is 200 kJ / mol or more larger than the oxygen separation energy of the first metal oxide.
  • X is an element that does not correspond to any of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements.
  • Element X 2 may be any element which corresponds to the above definition, but is not imposed specifically limited otherwise, preferably titanium (Ti). Further, tungsten (W) also can be used as the element X 2.
  • oxides of elements X 2 in the semiconductor layer is a semiconductor layer, a low density at the central portion, having a concentration gradient of high concentration both interfaces. That is, the at least one element X 2 concentration shows a minimum value at the central portion in the thickness direction of the semiconductor layer.
  • the concentration of the oxide of the element X 2 is preferably to have a minimum value in the central portion in the thickness direction of the semiconductor layer approaches from there to both interfaces, Each preferably has a monotonically increasing concentration gradient.
  • concentration of the oxide of the element X 2 in both interfaces from the viewpoint of for increasing the mobility is preferably 20 wt% or less 1 wt% or more.
  • concentration of the oxide of the element X 2 in the central portion is not particularly limited as long as it is substantially lower than the concentration at both interfaces, and is preferably 0.1% by weight or less, for example, substantially zero. It is particularly preferred that
  • the concentration of the element X 2 at both interfaces is high, the contact resistance at the interface between the source electrode and / or the drain electrode and the semiconductor layer is low, the electron mobility is high, and the gate controllability. It is possible to realize a practically preferable characteristic of being excellent in resistance. Due to the high concentration of element X 2 (for example, titanium) in the composite oxide constituting the semiconductor layer at the interface between the source electrode and / or drain electrode and the semiconductor layer, the composite oxide tends to release oxygen. Will have. As a result, the complex oxide in the vicinity of the interface with the source electrode and / or drain electrode generates oxygen vacancies and is so-called metalized, and the contact resistance with the source electrode and / or drain electrode is reduced.
  • element X 2 for example, titanium
  • the concentration of the element X 2 (for example, titanium) in the complex oxide constituting the semiconductor layer is high, the electron mobility tends to be improved. Effect more susceptible to the gate voltage, in the vicinity of the interface between the gate electrode side of the insulating film layer, by a high high electron mobility concentration of the element X 2 of the semiconductor layer to control a higher current at the same gate voltage In other words, an effect that gate controllability is improved can be realized.
  • the layer structure and other structures of the thin film transistor of the second invention of the present application are the same as those of the first invention of the present application.
  • the above description of the structure of the first invention of the present application also applies to the second invention of the present application as long as it does not contradict the purpose of the second invention of the present application.
  • the concentration of at least one element X 1 selected from the group consisting of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements among the elements X constituting the second oxide is the semiconductor layer.
  • at least one element that does not correspond to any of silicon, tantalum, zirconium, hafnium, aluminum, yttrium, and rare earth elements among the elements X constituting the second oxide is the semiconductor layer.
  • the concentration of X 2 indicates a minimum value at the central portion in the thickness direction of the semiconductor layer.
  • the concentration of silicon that corresponds to the element X 1 represents a maximum value in the central portion in the thickness direction of the semiconductor layer
  • the concentration of titanium corresponding to the element X 2 is the thickness direction of the semiconductor layer
  • a minimum value may be shown at the center.
  • the silicon concentration at the central portion of the semiconductor layer exhibits a maximum value, thereby realizing a target effect of suppressing characteristic deterioration such as a shift in threshold current due to light irradiation, and both of the semiconductor layers.
  • the high titanium concentration at the interface realizes the effect that the contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer is low, the electron mobility is high, and the gate controllability is excellent.
  • a thin film transistor having characteristics at a high level can be realized.
  • the thin film transistor of the third invention of the present application A source electrode and a drain electrode; A semiconductor layer provided in contact with the source electrode and the drain electrode; A gate electrode provided corresponding to a channel between the source electrode and the drain electrode; A thin film transistor having an insulator layer provided between the gate electrode and the semiconductor layer,
  • the semiconductor layer has a second metal oxide that can generate electron carriers by introducing oxygen vacancies, and the second energy of oxygen is 200 kJ / mol or more higher than that of the first metal oxide.
  • the semiconductor layer further contains nitrogen, and the concentration of nitrogen shows a maximum value in a central portion in the thickness direction of the semiconductor layer.
  • the semiconductor layer further contains nitrogen, and the concentration of nitrogen exhibits a maximum value at the central portion in the thickness direction of the semiconductor layer.
  • the concentration of nitrogen exhibits a maximum value at the central portion in the thickness direction of the semiconductor layer.
  • the said semiconductor layer contains nitrogen further, and the density
  • the concentration of Si 3 N 4 (+2.4 eV) that can have the effect of expanding the band gap in addition to the above-described effect on the nitrogen concentration distribution has a maximum value in the central portion in the thickness direction of the semiconductor layer. Therefore, as in the first invention of the present application, a technical effect that characteristic deterioration such as shift of threshold current due to light irradiation is suppressed can be realized.
  • the addition of the second oxide to the semiconductor layers of the first to third inventions of the present application can be appropriately performed by employing a conventionally known method.
  • the second oxide is an oxide of a nonmetallic element such as boron or carbon
  • the specific example of the case where the first metal oxide is indium oxide (In 2 O 3 ) is described below. explain.
  • the first metal oxide is indium oxide (In 2 O 3 ) and the second oxide is boron (B) oxide
  • the boron oxide is added to the indium oxide, for example, by ion implantation.
  • the addition amount and depth can be controlled by changing the acceleration voltage.
  • the content is more preferably greater than 0 and 10% by weight or less.
  • ion implantation is performed by implanting boron ions instead of boron oxide into the first metal oxide.
  • This boron ion becomes a boron oxide in the first metal oxide.
  • the oxide can also be formed inside the first metal oxide.
  • the addition in the form of the oxide in the first metal oxide may be referred to as “adding the oxide”. Please be careful.
  • the addition of carbon oxide to indium oxide is, for example, In 2 O 3. It can be carried out by a co-sputtering method using a target and a graphite target. By changing the ratio of each sputtering power, the amount of carbon oxide added can be controlled, and the content is more preferably greater than 0 and not more than 10% by weight.
  • both the first metal oxide described first and the non-metal oxide described here were simultaneously used. It is also possible to form the semiconductor layer 50 with a composite metal oxide.
  • the second metal oxide and the non-metal oxide of the second type are included in the semiconductor layer made of the composite metal oxide. Two oxides may inevitably coexist. For example, when a thin film of such a semiconductor layer is manufactured by a solution method such as a sol-gel method, there is a high possibility that carbon remains in the thin film. It should be noted that such a case is also included in the first to third inventions of the present application.
  • examples of physical vapor deposition include vapor deposition and sputtering.
  • Examples of the vapor deposition method include vacuum vapor deposition, molecular beam vapor deposition (MBE), ion plating, and ion beam vapor deposition.
  • Examples of the sputtering method include conventional sputtering, magnetron sputtering, ion beam sputtering, ECR (electron cyclotron resonance) sputtering, and reactive sputtering.
  • a film forming method such as a reactive sputtering method, a DC (direct current) sputtering method, or a radio frequency (RF) sputtering method can be used.
  • the gate electrode 30 and the insulator layer 40 are formed on the substrate 20 by a generally known method, and then the semiconductor layer 50 is formed.
  • the semiconductor layer 50 includes the first metal oxide powder and the second oxide powder having an oxygen separation energy of 200 kJ / mol or more larger than the oxygen separation energy of the first metal oxide. Is produced by a physical vapor deposition method using a target that is a sintered body including a mixed gas of a rare gas and oxygen. Here, it demonstrates as using sputtering method as a physical vapor deposition method.
  • a sintered body of indium oxide powder and silicon oxide powder may be employed as the target.
  • the target may be mixed with impurities such as an additive (metal oxide or the like) at a weight percent or less of silicon oxide.
  • impurities such as an additive (metal oxide or the like) at a weight percent or less of silicon oxide.
  • metal oxides such as zinc oxide
  • indium oxide and silicon oxide may be mixed into the target at a ratio (weight ratio) equal to or lower than the silicon oxide content in the entire target as unintended impurities. Absent.
  • the content of silicon oxide contained in the sintered body is preferably more than 0% by weight and 50% by weight or less. Moreover, it is more preferable that the content of silicon oxide is more than 0 wt% and not more than 5 wt%.
  • In-Zn-O-based and In-Ga-Zn-O-based metal oxides which are generally known oxide semiconductors, if indium oxide is the "host material” and zinc oxide or gallium oxide is the “guest material” In general, 20 to 30% of guest material (zinc oxide or gallium oxide) is mixed with the host material (indium oxide).
  • the semiconductor layer 50 of the thin film transistor 10 of the present embodiment is formed into a thin film using the sintered body as described above as a target.
  • the silicon oxide content is more preferably more than 0 wt% and 5 wt% or less. Therefore, the semiconductor layer 50 in this preferable composition is used.
  • the oxide semiconductor can have an extremely small content of the guest material (silicon oxide) with respect to the host material (indium oxide) as compared with a conventionally known oxide semiconductor.
  • a mixed gas of a rare gas and oxygen may be used as a process gas.
  • the rare gas include helium, neon, argon, krypton, and xenon.
  • the process gas preferably does not contain a compound having a hydrogen atom.
  • an amorphous semiconductor layer can be formed by performing a step of forming a semiconductor layer at 10 ° C. or higher and 200 ° C. or lower. Further, by performing the treatment at a temperature higher than 200 ° C. and lower than or equal to 400 ° C., a suitable crystallized semiconductor layer can be formed. Further, the step of forming the semiconductor layer may be performed at room temperature.
  • “implemented at room temperature” means that the semiconductor layer is not heated for the step of forming the semiconductor layer, and the temperature adjustment of the working environment is unnecessary.
  • sputtering method employed in the method for manufacturing the thin film transistor of the present embodiment known methods such as RF sputtering and DC sputtering can be used.
  • the target may be indium oxide powder and silicon oxide powder, and a mixture of these powders may be sintered.
  • a sintered body of each powder may be sufficient. The latter is preferable from the viewpoint of controllability of the concentration distribution of silicon oxide as the second oxide.
  • the semiconductor layer can be formed by co-sputtering using a plurality of sintered bodies.
  • the concentration distribution of elements X 1 in the first invention, the concentration distribution of elements X 2 in the present second invention also, it is possible to preferably control by co sputtering.
  • the concentration distribution of Si and Ti in the In—Si—Ti—O semiconductor layer is expressed by the In—Si—O target and the In—Ti—O target.
  • both targets are installed in the same chamber, and the sputtering power for each target is preferably adjusted by preferably changing continuously.
  • the semiconductor layer can be formed in a process range corresponding to the magnitude of the separation energy of oxygen.
  • the effects of the first to third inventions of the present application are appropriately achieved by using the semiconductor layer in which the concentration distribution of the specific oxide is appropriately controlled. It is possible to realize a gate that suppresses deterioration of characteristics such as threshold current shift due to light irradiation, has low contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer, and has high electron mobility. There is provided a thin film transistor having a practically preferable characteristic of excellent controllability at a high level.
  • the first to third inventions of the present application can also be applied to a so-called top gate type thin film transistor. Details of the structure and manufacturing method of a so-called top gate type thin film transistor are well known in the art as described in, for example, Japanese Patent Application Laid-Open No. 2013-219936, and based on these, those skilled in the art can apply the present application without undue trial and error.
  • the first to third inventions can be implemented in a top gate type embodiment.
  • a so-called top contact type thin film transistor has been described.
  • the first to third inventions of the present application can also be applied to a so-called bottom contact type thin film transistor. Details of the structure and manufacturing method of so-called bottom contact type thin film transistors are also well known in the art, and those skilled in the art can implement the first to third aspects of the present invention in a bottom contact type mode without undue trial and error. Is possible.
  • the oxygen separation energy of the metal oxide to be added is the oxygen separation energy of the tin oxide. Based on the new knowledge of the present inventors that the amount of oxygen deficiency in the above problem can be controlled by making the difference from the energy of separation of oxygen with respect to tin oxide less than 200 kJ / mol.
  • the thin film transistor of the first embodiment and the manufacturing method thereof are provided.
  • the present inventors further add an additional oxide whose oxygen separation energy is smaller than that of tin oxide, and the addition amount is less than the addition amount of the above metal oxide.
  • the present inventors have found that the amount of oxygen vacancies can be controlled and the amorphous stable formation temperature range can be expanded.
  • the fourth invention of the present application also provides a thin film transistor and a manufacturing method thereof according to the second embodiment based on this finding.
  • the thin film transistor of the first embodiment is provided corresponding to a source electrode and a drain electrode, a semiconductor layer provided in contact with the source electrode and the drain electrode, and a channel between the source electrode and the drain electrode.
  • the semiconductor layer of the thin film transistor of the first embodiment further includes an additional oxidation in which the oxygen separation energy is smaller than that of tin oxide and the addition amount is smaller than that of the above metal oxide. It is a composite metal oxide to which a product is added.
  • the method for manufacturing a thin film transistor of this embodiment includes a step of forming the semiconductor layer at 10 ° C. or higher and 500 ° C. or lower when manufacturing the thin film transistor.
  • FIG. 8 is a schematic cross-sectional view of the thin film transistor 201 according to the first embodiment.
  • the substrate 202 a substrate formed using a known forming material can be used, and any of those having light transmittance and those having no light transmittance can be used.
  • an inorganic substrate made of alkali silicate glass, quartz glass, silicon nitride, or the like; a silicon substrate; a metal substrate whose surface is insulated; acrylic resin, polycarbonate resin, PET (polyethylene terephthalate), or PBT (polybutylene)
  • Various substrates such as a resin substrate made of a polyester resin such as terephthalate) or a paper substrate can be used.
  • the substrate may be a composite material formed by combining a plurality of these materials.
  • the thickness of the substrate 202 can be appropriately set according to the design.
  • the thin film transistor 201 is a so-called bottom gate type transistor.
  • the thin film transistor 201 includes a gate electrode 203 provided over a substrate 202, an insulator layer 204 provided to cover the gate electrode 203, a semiconductor layer 205 provided on the top surface of the insulator layer 204, A source electrode 208 and a drain electrode 209 are provided in contact with the semiconductor layer 205 on the upper surface.
  • the gate electrode 203 is provided so as to correspond to the channel region of the semiconductor layer 205 (at a position overlapping the channel region in plan view).
  • the semiconductor layer 205 is composed of a composite metal oxide obtained by adding a metal oxide 207 to tin oxide 206.
  • the semiconductor layer may contain components other than the metal oxide 207 and inevitable impurities as long as the adverse effects of the fourth invention of the present application are not adversely affected.
  • the semiconductor layer 205 can be seen as if particles of the metal oxide 207 are scattered in the tin oxide 206.
  • the metal oxide is actually uniformly added to the tin oxide, that is, doped, so that the composite metal oxide becomes a uniform material.
  • the gate electrode 203, the source electrode 208, and the drain electrode 209 those formed of a generally known material can be used.
  • the material for forming these electrodes include aluminum (Al), gold (Au), silver (Ag), copper (Cu), nickel (Ni), molybdenum (Mo), tantalum (Ta), and tungsten (W).
  • the material for forming these electrodes include aluminum (Al), gold (Au), silver (Ag), copper (Cu), nickel (Ni), molybdenum (Mo), tantalum (Ta), and tungsten (W).
  • metal materials such as these, alloys thereof, and conductive oxides such as indium tin oxide (ITO) and zinc oxide (ZnO).
  • these electrodes may form the laminated structure of two or more layers, for example by plating the surface with a metal material.
  • the gate electrode 203, the source electrode 208, and the drain electrode 209 may be formed of the same forming material, or may be formed of different forming materials.
  • the source electrode 208 and the drain electrode 209 are preferably made of the same material since manufacturing is easy.
  • the insulator layer 204 has an insulating property, and can be formed using either an inorganic material or an organic material as long as the gate electrode 203 can be electrically insulated from the source electrode 208 and the drain electrode 209. It may be formed.
  • the inorganic material include normally known insulating oxides such as SiO 2 , SiN x , SiON, Al 2 O 3 , and HfO 2 , nitrides, and oxynitrides.
  • the organic material include acrylic resin, epoxy resin, silicon resin, and fluorine resin.
  • the organic material is preferably a photocurable resin material because it is easy to manufacture and process.
  • the semiconductor layer 205 is obtained by adding, to tin oxide, a metal oxide in which the dissociation energy of oxygen is larger than the separation energy of oxygen in tin oxide and the difference in separation energy between the two is smaller than 200 kJ / mol.
  • tin oxide (SnO 2 ) is used as the first metal oxide in the above-mentioned prior application of the present inventors.
  • the separation energy of oxygen of tin oxide is as small as 528 kJ / mol, oxygen from tin oxide is reduced. Almost desorbs and easily generates oxygen deficiency.
  • the amount of oxygen vacancies becomes too large, it changes from semiconducting properties to metallic properties, making it unsuitable as a semiconductor layer.
  • the inventors of the present application added a metal oxide having an oxygen separation energy larger than that of tin oxide in order to control the oxygen deficiency of tin oxide.
  • the metal oxide that can be added include samarium oxide having an oxygen separation energy of 573 kJ / mol, tungsten oxide of 720 kJ / mol, neodymium oxide of 703 kJ / mol, and gadolinium oxide of 715 KJ / mol.
  • the content of the metal oxide added to make tin oxide a semiconductor layer having an appropriate oxygen deficiency is preferably in the range of greater than 0 to 50% by weight.
  • the semiconductor layer can be manufactured at a low temperature of 300 ° C. or less.
  • In-Zn-O-based and In-Ga-Zn-O-based metal oxides tend to be polycrystalline when a semiconductor layer is formed. Therefore, in a generally known thin film transistor, the surface of the semiconductor layer does not become flat due to crystal grains contained in the semiconductor layer. In addition, the normally known semiconductor layer of an oxide film transistor has a reduced electrical conductivity in the plane direction due to such crystal grains. Therefore, in order to obtain planarization of the surface of the semiconductor layer and high electrical conductivity, the semiconductor layer preferably has an amorphous structure.
  • the thickness of the semiconductor layer 205 is more preferably in the range of 5 nm to 20 nm.
  • the thickness of the semiconductor layer 205 was measured using a crystal oscillation type film thickness meter disposed mainly for film thickness calibration in the sputtering chamber in which the semiconductor layer 205 was formed.
  • the composite metal oxide constituting the semiconductor layer 205 is obtained by adding the above-described metal oxide to tin oxide, and further having an oxygen separation energy smaller than that of tin oxide.
  • an additional oxide having an addition amount smaller than that of the metal oxide is added. The inventors of the present application have found that the semiconductor layer becomes amorphous even in a high temperature range of 500 ° C. by controlling the amount of oxygen vacancies by adding a metal oxide and adding an additional oxide.
  • lead oxide having an oxygen release energy of 382.4 ⁇ 3.3 kJ / mol
  • palladium oxide having 238.1 ⁇ 12.6 kJ / mol
  • 418.6 ⁇ 11.6 kJ / mol mol
  • platinum oxide 517.90 ⁇ 0.05 kJ / mol sulfur oxide
  • 434 ⁇ 42 kJ / mol antimony oxide
  • 426.3 ⁇ 6.3 kJ / mol strontium oxide 213 ⁇ 84 kJ / mol thallium oxide, 387 7 ⁇ 10 kJ / mol ytterbium oxide and the like.
  • the thin film transistor 201 ′ of the second embodiment of the present invention shown in FIG. 9 has basically the same structure as the thin film transistor 201 of FIG. 8, but the semiconductor layer 205 ′ corresponding to the semiconductor layer 205 of FIG. It is a composite metal oxide in which the metal oxide 207 is added to the tin 206, and an additional oxide 210 in which the oxygen separation energy is smaller than that of the tin oxide and the addition amount is smaller than that of the metal oxide. . 9 that have the same reference numerals as the elements in FIG. 8 are the same as the corresponding elements in FIG. 8, and therefore, the description thereof is omitted.
  • the semiconductor layer 205 ′ (composite metal oxide) is made of tin oxide 206 for convenience of illustration also in FIG. 9. It is drawn in a form that can be seen as interspersed with additional oxides 210, but here again, these oxides are actually uniformly added or doped in the tin oxide. Therefore, it should be noted that the composite metal oxide is a uniform material.
  • the addition of the metal oxide tungsten oxide (WO 3 ) and the additional oxide ytterbium oxide (Yb 2 O 3 ) to the tin oxide (SnO 2 ) is performed, for example, at the target preparation stage of the sputtering method.
  • the addition amount can be controlled by changing the ratio of sputtering power by co-sputtering method using Sn—W—O target and Yb 2 O 3 target, and the content is larger than 0 and 10% by weight. The following is more preferable.
  • the semiconductor layer of the thin film transistor of this embodiment can also be formed by using physical vapor deposition (or physical vapor deposition).
  • examples of physical vapor deposition include vapor deposition and sputtering.
  • Examples of the vapor deposition method include vacuum vapor deposition, molecular beam vapor deposition (MBE), ion plating, and ion beam vapor deposition.
  • Examples of the sputtering method include conventional sputtering, magnetron sputtering, ion beam sputtering, ECR (electron cyclotron resonance) sputtering, and reactive sputtering.
  • a film forming method such as a reactive sputtering method, a DC (direct current) sputtering method, or a radio frequency (RF) sputtering method can be used.
  • the gate electrode 203 and the insulator layer 204 are formed on the substrate 202 by a generally known method, and then the semiconductor layer 205 is formed.
  • the semiconductor layer 205 includes a tin oxide powder and a metal oxide having an oxygen separation energy larger than that of the tin oxide, and the oxygen of the tin oxide and the metal oxide. It is manufactured by a physical vapor deposition method using a target which is a sintered body containing a powder having a difference in separation energy of less than 200 kJ / mol and a mixed gas of a rare gas and oxygen.
  • sputtering method as a physical vapor deposition method.
  • a sintered body of a tin oxide powder and a tungsten oxide powder may be employed as the target.
  • the target may be mixed with impurities such as an additive (metal oxide or the like) at a mass% or less of tungsten oxide.
  • impurities such as an additive (metal oxide or the like) at a mass% or less of tungsten oxide.
  • a metal oxide (such as zinc oxide) other than tin oxide and tungsten oxide may be mixed into the target at a ratio (weight ratio) equal to or lower than the tungsten oxide content in the target as an unintended impurity. .
  • the content of tungsten oxide contained in the sintered body is preferably more than 0 mass% and 50 mass% or less. Further, the content of tungsten oxide is more preferably 0% by mass to 5% by mass.
  • In-Zn-O-based and In-Ga-Zn-O-based metal oxides which are generally known oxide semiconductors, if indium oxide is the "host material” and zinc oxide or gallium oxide is the “guest material”
  • the guest material zinc oxide or gallium oxide
  • the guest material is mixed with 20-30% of the host material (indium oxide).
  • the semiconductor layer 205 of the thin film transistor 201 of the present embodiment is formed into a thin film using the sintered body as described above as a target.
  • the content of tungsten oxide is more preferably 0% by mass to 5% by mass, and thus the semiconductor layer 205 in the case of this preferable composition.
  • This oxide semiconductor has an extremely small content of the guest material (tungsten oxide) with respect to the host material (tin oxide) as compared with a conventionally known oxide semiconductor.
  • a mixed gas of a rare gas and oxygen is used as a process gas.
  • the rare gas include helium, neon, argon, krypton, and xenon.
  • the process gas does not include a compound having a hydrogen atom.
  • an amorphous semiconductor layer can be formed by performing a step of forming a semiconductor layer at 10 ° C. to 300 ° C.
  • a suitable crystallized semiconductor layer can be formed by performing the process at a temperature higher than 300 ° C. and lower than or equal to 500 ° C.
  • the step of forming the semiconductor layer is preferably performed at room temperature.
  • “implemented at room temperature” means that the semiconductor layer is not heated for the step of forming the semiconductor layer, and the temperature adjustment of the working environment is unnecessary.
  • sputtering method employed in the method for manufacturing the thin film transistor of the present embodiment known methods such as RF sputtering and DC sputtering can be used.
  • the target may be a sintered body of a mixture of these powders or a sintered body of each powder as long as tin oxide powder and tungsten oxide powder are used.
  • the semiconductor layer can be formed by co-sputtering using a plurality of sintered bodies.
  • silicon oxide has been described as the metal oxide, samarium oxide (Sm—O), tungsten oxide (W—O), neodymium oxide (Nd—O), and gadolinium oxide (Gd—O) were used instead. Even in this case, the semiconductor layer can be formed in a process range corresponding to the magnitude of the separation energy of oxygen.
  • the semiconductor layer 205 is formed after the gate electrode 203 and the insulator layer 204 are formed on the substrate 202 by a generally known method.
  • the semiconductor layer 205 has a difference of 200 kJ between the tin oxide powder and the oxygen separation energy of the tin oxide, and the oxygen separation energy of the tin oxide is 200 kJ.
  • a physical vapor deposition method using a target that is a sintered body containing a noble gas and a mixed gas of oxygen and oxygen.
  • a target may be a sintered body of a tin oxide powder, a tungsten oxide powder, and a ytterbium oxide powder. Further, the amount of ytterbium oxide added to the target is always smaller than the amount of tungsten oxide added.
  • the content of tungsten oxide contained in the sintered body is more than 0% by mass and 50% by mass or less
  • the content of ytterbium oxide is more than 0% by mass and less than 20% by mass.
  • the content of ytterbium oxide is more preferably 0% by mass to 4% by mass.
  • a mixed gas of a rare gas and oxygen is used as a process gas.
  • the rare gas include helium, neon, argon, krypton, and xenon.
  • the process gas does not include a compound having a hydrogen atom.
  • the process of forming the semiconductor layer is 10 ° C. or higher, as studied by the inventors. It was found that an amorphous semiconductor layer can be formed by carrying out at 500 ° C. or lower. Further, the step of forming the semiconductor layer is preferably performed at room temperature.
  • “implemented at room temperature” means that the semiconductor layer is not heated for the step of forming the semiconductor layer, and the temperature adjustment of the working environment is unnecessary.
  • sputtering method employed in the method for manufacturing the thin film transistor of the present embodiment known methods such as RF sputtering and DC sputtering can be used.
  • the characteristic change is suppressed by using the novel composite metal oxide for the semiconductor layer.
  • the semiconductor device having the above configuration it has a thin film transistor in which the characteristic change is suppressed, and has high reliability.
  • a thin film transistor in which a change in characteristics is suppressed can be easily manufactured by using a novel composite metal oxide for a semiconductor layer.
  • the fourth invention of the present application can also be applied to a so-called top gate type thin film transistor.
  • a so-called top contact type thin film transistor has been described.
  • the fourth invention of the present application can also be applied to a so-called bottom contact type thin film transistor.
  • the thin film transistor using an oxide semiconductor according to the fifth invention of the present application corresponds to a source electrode and a drain electrode, a semiconductor layer provided in contact with the source electrode and the drain electrode, and a channel between the source electrode and the drain electrode.
  • An oxidation in which oxygen vacancies are introduced comprising: a first metal oxide made of a material; and a second oxide having an oxygen separation energy greater than that of the first metal oxide by 200 kJ / mol or more.
  • the method for manufacturing a thin film transistor using an oxide semiconductor according to the fifth aspect of the present invention includes a step of forming the semiconductor layer at 10 ° C. or higher and 400 ° C. or lower when manufacturing the thin film transistor. You may have the process of forming the said semiconductor layer at 10 degreeC or more and 200 degrees C or less.
  • FIG. 15 is a schematic cross-sectional view showing an embodiment of a thin film transistor using an oxide semiconductor according to the fifth invention.
  • a thin film transistor 310 in FIG. 15 is a so-called bottom-gate transistor.
  • the thin film transistor 310 includes a gate electrode 330 provided on a substrate 320, an insulator layer (gate insulator layer) 340 provided so as to cover the gate electrode 330, and an insulator layer.
  • a substrate formed of a known forming material can be used, and any of those having light transmittance and those having no light transmittance may be used.
  • a material for forming the substrate 320 for example, an inorganic substrate made of alkali silicate glass, quartz glass, silicon nitride, or the like; a silicon substrate; a metal substrate with an insulating surface; acrylic resin, polycarbonate resin, PET ( Various substrates such as a resin substrate made of a polyester resin such as polyethylene terephthalate) or PBT (polybutylene terephthalate); a paper substrate can be used. Further, the substrate may be a composite material formed by combining a plurality of these materials. Further, the thickness of the substrate 320 can be appropriately set according to the design.
  • the gate electrode 330 is provided so as to correspond to the channel region of the semiconductor layer 350 (at a position overlapping the channel region in plan view). That is, the channel region of the semiconductor layer 350 is in a region corresponding to the position of the gate electrode 330.
  • the semiconductor layer of the thin film transistor mainly functions as a channel on the gate electrode side.
  • MoW is used as the gate electrode 330.
  • the semiconductor layer 350 is formed of the oxide semiconductor of the fifth invention of the present application.
  • the semiconductor layer 350 includes a first metal oxide made of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and an oxygen separation energy of the first metal oxide.
  • An oxide semiconductor having an oxygen deficient portion which is formed from a second oxide greater than the energy by 200 kJ / mol or more, and the oxygen deficient portion further includes an OH group, an H group, an F group, a Cl group, Alternatively, it is formed by the oxide semiconductor in which the first metal oxide and the substituent are bonded by being substituted by at least one selected from the group consisting of B groups.
  • the semiconductor layer 350 may contain components other than these and unavoidable impurities.
  • the first metal oxide is a substance having a semiconductor property capable of generating electron carriers by introducing oxygen vacancies.
  • the first metal oxide is preferably a metal oxide containing at least one selected from the group consisting of indium, gallium, zinc, and tin
  • the second oxide is preferably zirconium (Zr). , Silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), hafnium (Hf), scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd) , Gadolinium (Gd), other rare earth elements, aluminum (Al), and carbon (C).
  • the oxide includes at least one selected from the group consisting of carbon (C).
  • the element of the second oxide is at least one selected from the group consisting of Zr, Pr, Si, Ti, W, Ta, La, Hf, and C.
  • the element of the first oxide is Sn
  • the element of the second oxide is at least one element selected from the group consisting of Sc, Ti, W, Nd, and Gd.
  • a metal oxide containing at least one of indium, zinc, and tin may be used.
  • indium that easily introduces oxygen vacancies at a low temperature may be used.
  • silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), lanthanum (La), hafnium (Hf), zirconium (Zr), and praseodymium (Pr) are used. It is also possible to use an oxide containing at least one selected from the group consisting of silicon (Si), titanium (Ti), tungsten (W), tantalum (Ta), lanthanum (La), and hafnium.
  • the second oxide it is an oxide containing at least one selected from the group consisting of (Hf).
  • an oxide containing carbon (C) can also be used.
  • the content of the second oxide may be greater than 0 and 50% by weight or less, greater than 0 and 10% by weight or less, and greater than 0 and 5% by weight or less.
  • the substituent introduced into the oxygen deficient portion is specifically selected from the group consisting of an OH group, an H group, an F group, a Cl group, or a B group. At least one is mentioned. In particular, an OH group and an H group are preferable, and an OH group is more preferable.
  • the content is preferably 0.1% or more and 10% or less, and when H groups are introduced, the content is preferably greater than 0% and 0.1% or less, F
  • the group, Cl group, or B group is introduced, the content is preferably more than 5 ⁇ 10 18 atoms / cm 3 and not more than 1 ⁇ 10 21 atoms / cm 3 .
  • the OH group content (%) is calculated by the formula [OH] / ([OH] + [O]) ⁇ 100, and the H group content (%) is [H] / ([H] + [ O]) ⁇ 100.
  • [OH], [H], and [O] represent atomic ratios of OH, H, and O in the oxide semiconductor, respectively.
  • the oxygen separation energy of indium oxide is as small as 346 ⁇ 30 kJ / mol, so oxygen is easily desorbed from indium oxide to generate oxygen vacancies. Easy to do. However, if the amount of oxygen vacancies becomes too large, it changes from semiconducting properties to metallic properties and becomes unsuitable as a semiconductor layer. As a result of repeated studies to solve this problem, the inventors of the present application added a second oxide having an oxygen separation energy larger than that of indium oxide in order to control the oxygen deficiency amount of indium oxide. I found out that I should do. Specifically, when an oxide having an oxygen separation energy of 725 kJ / mol or more, more preferably 780 kJ / mol or more is used as the second oxide, the amount of oxygen deficiency of indium oxide can be easily controlled.
  • the oxygen separation energy of the second oxide is 200 kJ / mol or more, more preferably 255 kJ / mol compared to the first metal oxide. What is larger than mol may be used. Therefore, the oxygen separation energy of the second oxide may be 255 kJ / mol or more larger than the oxygen separation energy of the first metal oxide.
  • the second oxide includes zirconium oxide (Zr—O), praseodymium oxide (Pr—O), lanthanum oxide (La—O), and silicon oxide (Si—O). Tantalum oxide (Ta—O), and hafnium oxide (Hf—O).
  • the second oxide is particularly 780 kJ / mol or more shown in Table C1.
  • the second oxide is more preferable. Specifically, lanthanum oxide (La—O), silicon oxide (Si—O), tantalum oxide (Ta—O), and hafnium oxide (Hf—O) can be given.
  • the oxygen separation energy of titanium oxide (Ti—O) is 666.5 ⁇ 5.6 kJ / mol
  • the oxygen separation energy of tungsten oxide (W—O) is 720 ⁇ 71 kJ / mol.
  • the content of the second oxide added to the first metal oxide in order to make the first metal oxide a semiconductor layer 350 having a suitable oxygen deficiency ranges from 0 to 50% by weight.
  • the content of the second oxide added to the first metal oxide is in the range of more than 0 and 5% by weight or less in terms of production at a low temperature of 200 ° C. or less.
  • the semiconductor layer 350 (that is, the oxide semiconductor forming the semiconductor layer 350) is preferably amorphous. In-Zn-O-based and In-Ga-Zn-O-based metal oxides tend to be polycrystalline when a semiconductor layer is formed. Therefore, in a generally known thin film transistor, the surface of the semiconductor layer does not become flat due to crystal grains contained in the semiconductor layer. In addition, the normally known semiconductor layer of an oxide film transistor has a reduced electrical conductivity in the plane direction due to such crystal grains. Therefore, in order to obtain planarization of the surface of the semiconductor layer and high electrical conductivity, the semiconductor layer 350 preferably has an amorphous structure.
  • the thickness of the semiconductor layer 350 (that is, the thickness of the oxide semiconductor forming the semiconductor layer 350) is preferably in the range of 5 nm to 20 nm. In the present embodiment, the thickness was measured using a crystal oscillation type film thickness meter disposed mainly for the purpose of film thickness calibration in the sputtering chamber in which the semiconductor layer 350 was formed.
  • the second oxide may include an oxide of carbon (C).
  • C an oxide of carbon
  • an element that forms an oxide having a larger separation energy than the first metal oxide may be added.
  • the oxide semiconductor into which oxygen vacancies are introduced may be one in which an oxide of carbon (C) is added to the first metal oxide. This is because the oxygen desorption energy of the C—O bond is as large as 1076.38 ⁇ 0.67 kJ / mol, so that the amount of oxygen deficiency introduced into the first metal oxide can be easily controlled.
  • the oxide When the oxide is added to the first metal oxide, it is not always necessary to add the oxide itself in the addition treatment operation itself. For example, a treatment for adding an element other than oxygen constituting the oxide is performed. An oxide can also be formed inside one metal oxide. Therefore, in the present application, regardless of the form of the addition treatment operation, the addition in the form of the oxide in the first metal oxide is referred to as “adding the oxide”. Please be careful.
  • the addition of carbon (C) to the first metal oxide indium oxide (In 2 O 3 ) is to change the ratio of the sputtering power by a co-sputtering method using an In 2 O 3 target and a graphite target.
  • the amount added can be controlled by the control, and the content is more preferably greater than 0 and 10% by weight or less. Therefore, the content of carbon (C) contained as the second oxide is preferably greater than 0 and 10% by weight or less.
  • the states of the first metal oxide and the second oxide in the semiconductor layer 350 are uniform (that is, uniform by adding or doping the second oxide into the first metal oxide uniformly). It is a substance).
  • the source electrode 360, the drain electrode 370, and a region that does not overlap with the source electrode 360 and the drain electrode 370 and corresponds to the position of the gate electrode 330 corresponds to a channel region.
  • the contact resistance is lowered by metallization.
  • the gate electrode 330 is provided so as to correspond to the channel region of the semiconductor layer 350 (at a position overlapping the channel region in a plan view).
  • the gate electrode 330, the source electrode 360, and the drain electrode 370 those formed of a generally known material can be used.
  • materials for forming these electrodes include aluminum (Al), gold (Au), silver (Ag), copper (Cu), nickel (Ni), molybdenum (Mo), tantalum (Ta), and tungsten (W).
  • metal materials such as these, alloys thereof, and conductive oxides such as indium tin oxide (ITO) and zinc oxide (ZnO).
  • these electrodes may form a laminated structure of two or more layers (for example, Ti / Al / Ti) by, for example, plating the surface with a metal material.
  • the gate electrode 330, the source electrode 360, and the drain electrode 370 may be formed of the same forming material, or may be formed of different forming materials. Since manufacture becomes easy, it is preferable that the source electrode 360 and the drain electrode 370 are the same formation material.
  • the insulator layer (gate insulator layer) 340 is an insulating material and an organic material as long as it has insulating properties and can electrically insulate the gate electrode 330 from the source electrode 360 and the drain electrode 370. Any of the materials may be used.
  • the inorganic material include normally known insulating oxides such as SiO 2 , SiN x , SiON, Al 2 O 3 , and HfO 2 , nitrides, and oxynitrides.
  • the organic material include acrylic resin, epoxy resin, silicon resin, and fluorine resin.
  • the organic material is preferably a photocurable resin material because it is easy to manufacture and process.
  • the insulator layer (gate insulator layer) 340 has a two-layer laminated structure in which a SiN layer is disposed at a contact portion of the substrate 320 and SiO 2 is disposed thereon.
  • This SiN layer can prevent the calcium, phosphorus, etc. generated from the substrate 320 from diffusing and deteriorating the semiconductor layer 350, and the SiO 2 disposed thereon is caused by the diffusion of nitrogen from the SiN layer. This is because deterioration of the semiconductor layer can be prevented.
  • the interlayer insulating film 380 has insulating properties, and can electrically insulate the source electrode 360, the drain electrode 370, and the source electrode 360 and the semiconductor layer 350 in a region not overlapping with the drain electrode 370. If so, it may be formed using either an inorganic material or an organic material.
  • the inorganic material include normally known insulating oxides such as SiO 2 , SiN x , SiON, Al 2 O 3 , and HfO 2 , nitrides, and oxynitrides.
  • the organic material include acrylic resin, epoxy resin, silicon resin, and fluorine resin. The organic material is preferably a photocurable resin material because it is easy to manufacture and process.
  • the oxide semiconductor of this embodiment can also be formed by using physical vapor deposition (or physical vapor deposition).
  • physical vapor deposition include vapor deposition and sputtering.
  • the vapor deposition method include vacuum vapor deposition, molecular beam vapor deposition (MBE), ion plating, and ion beam vapor deposition.
  • the sputtering method examples include conventional sputtering, magnetron sputtering, ion beam sputtering, ECR (electron cyclotron resonance) sputtering, and reactive sputtering.
  • a film forming method such as a reactive sputtering method, a DC (direct current) sputtering method, or a radio frequency (RF) sputtering method can be used.
  • the first metal oxide composed of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and the oxygen separation energy of the first metal oxide is greater than the oxygen separation energy of the first metal oxide.
  • an oxide semiconductor having an oxygen deficient portion which is formed from a second oxide that is greater than or equal to 200 kJ / mol, is formed.
  • a target that is a sintered body including a first metal oxide powder and an oxide powder having an oxygen separation energy of 200 kJ / mol or more larger than the oxygen separation energy of the first metal oxide; It is manufactured by a physical vapor deposition method using a mixed gas of a rare gas and oxygen.
  • sputtering method as a physical vapor deposition method.
  • a first metal oxide composed of a metal oxide capable of generating electron carriers by introducing oxygen vacancies
  • the oxygen separation energy of the first metal oxide is 200 kJ / mol or more larger than the oxygen separation energy of the first metal oxide.
  • the target is an indium oxide powder and a silicon oxide powder. It is preferable to employ a sintered body.
  • the target may be mixed with impurities such as an additive (metal oxide or the like) at a weight percent or less of silicon oxide.
  • metal oxides such as zinc oxide
  • indium oxide and silicon oxide may be mixed into the target at a ratio (weight ratio) equal to or lower than the silicon oxide content in the entire target as unintended impurities. Absent.
  • the content of silicon oxide contained in the sintered body is preferably more than 0% by weight and 50% by weight or less. Further, the content of silicon oxide is more preferably more than 0 wt% and not more than 5 wt%.
  • In-Zn-O-based and In-Ga-Zn-O-based metal oxides which are generally known oxide semiconductors, if indium oxide is the "host material” and zinc oxide or gallium oxide is the “guest material”
  • the guest material zinc oxide or gallium oxide
  • the guest material is mixed with 20-30% of the host material (indium oxide).
  • the silicon oxide content is more preferably more than 0 wt% and not more than 5 wt% as described above. Therefore, the semiconductor layer in this preferred composition
  • the 350 oxide semiconductor has an extremely small content of the guest material (silicon oxide) with respect to the host material (indium oxide) as compared with a conventionally known oxide semiconductor.
  • a mixed gas of a rare gas and oxygen is used as a process gas.
  • the rare gas include helium, neon, argon, krypton, and xenon.
  • the process gas does not include a compound having a hydrogen atom.
  • the first metal oxide composed of a metal oxide capable of generating electron carriers by introducing oxygen vacancies, and the oxygen separation energy.
  • an oxide semiconductor having an oxygen deficient portion which is formed from a second oxide having a larger oxygen dissociation energy than the first metal oxide by 200 kJ / mol or more, indium oxide and silicon oxide are used.
  • a target including the oxide semiconductor it has been found that a high temperature is not required to make the metal oxide constituting the oxide semiconductor an amorphous film.
  • an amorphous oxide semiconductor is formed by performing the step of forming an In—Si—O system into which oxygen vacancies are introduced at 10 ° C. or higher and 200 ° C. or lower. can do.
  • a suitable crystallized oxide semiconductor can be formed.
  • the step of forming the oxide semiconductor is preferably performed at room temperature.
  • “implemented at room temperature” means non-heating for the step of forming an oxide semiconductor, and does not require temperature adjustment of the working environment.
  • sputtering method employed in the method for manufacturing an oxide semiconductor according to this embodiment known methods such as RF sputtering and DC sputtering can be used.
  • the target may be a sintered body of a mixture of these powders or a sintered body of each powder, as long as the target uses indium oxide powder and silicon oxide powder.
  • a sintered body is formed for each metal oxide powder, an oxide semiconductor in which the amount of oxygen vacancies is controlled by co-sputtering using a plurality of sintered bodies can be formed.
  • Silicon oxide has been described as the second oxide, but instead zirconium oxide (Zr—O), praseodymium oxide (Pr—O), lanthanum oxide (La—O), tantalum oxide (Ta—O), and oxidation Even when hafnium (Hf—O) is used, an oxide semiconductor in which the amount of oxygen vacancies is controlled can be formed in a process range corresponding to the magnitude of the separation energy of oxygen.
  • a substituent is introduced into the oxygen deficient portion of the oxide semiconductor having the oxygen deficient portion thus manufactured.
  • the substituent to be introduced at least one selected from the group consisting of OH group, H group, F group, Cl group, or B group can be used.
  • an OH group is introduced into the oxygen deficient part, it is introduced by heat treatment under high humidity. For example, it sealed 80% or more high humidity of introducing H 2 O gas into the quartz reaction vessel, at a temperature range of 300 ° C. from 0.99 ° C., introduced by heat treatment.
  • H group into the oxygen deficient portion it is introduced by heat treatment in an H 2 atmosphere gas. For example, it is introduced by annealing at 300 to 400 ° C. under H 2 atmosphere gas.
  • an F group, a Cl group, or a B group is introduced into the oxygen deficient portion, it is introduced by ion implantation (ion implantation) or a plasma treatment method.
  • the gate electrode 330 and the insulator layer (gate insulator layer) 340 are formed on the substrate 320 by a generally known method, and then the semiconductor is formed on the upper surface of the insulator layer 340.
  • Layer 350 is formed.
  • the semiconductor layer 350 is formed using an oxide semiconductor manufactured by the above-described manufacturing method.
  • the gate electrode 330 is provided so as to correspond to the channel region of the semiconductor layer 350 (at a position overlapping the channel region in a plan view).
  • the source electrode 360 and the drain electrode 370 are provided on the semiconductor layer 350 so that a part of the semiconductor layer 350 overlaps the source electrode 360 and the drain electrode 370 by a generally known method, and further, the whole (specifically, Covers the source electrode 360, the drain electrode 370, and the semiconductor layer 350 in a region not overlapping with the source electrode 360 and the drain electrode 370, with the interlayer insulating film 380. In this manner, the thin film transistor 310 with high reliability with respect to light irradiation from the light emitting layer can be manufactured.
  • the change in characteristics is suppressed by using a novel oxide semiconductor for the semiconductor layer.
  • the semiconductor device using the thin film transistor having such a structure has high reliability because it has a thin film transistor in which the characteristic change is suppressed.
  • a thin film transistor in which a change in characteristics is suppressed by using a novel oxide semiconductor for a semiconductor layer can be easily manufactured.
  • Example A1 In this example, the thin film transistor shown in FIG. 2 was manufactured and the operation was confirmed.
  • the thin film transistor shown in the figure has substantially the same configuration as that of the thin film transistor 10 shown in FIG. 1, and instead of the gate electrode 30 included in the thin film transistor 10 shown in FIG. Is used.
  • the thin film transistor of the example uses a Si substrate doped with a p-type impurity, forms the insulator layer 24 by oxidizing the surface, and then forms the semiconductor layer 25 on the surface of the insulator layer 24 using a method described later. It was manufactured by doing.
  • the source electrode 26 and the drain electrode 27 were formed by mask vapor deposition on the surface of the semiconductor layer 25.
  • the source electrode 26 and the drain electrode 27 were made of gold (Au) as a forming material and had a thickness of 50 nm. Further, the separation distance (gate length) between the source electrode 26 and the drain electrode 27 was 350 ⁇ m, and the length of the facing portion was 940 ⁇ m.
  • the oxide semiconductor layer 25 uses an In—Si—O target with a SiO 2 concentration of 10% by weight and an In—Ti—O target with a Ti concentration of 10% by weight.
  • Flow rate: O 2 / Ar 3 sccm / 20 sccm, degree of vacuum 0.25 Pa, without heating, as shown in Table A3, continuously changing the sputtering power for each target according to the film thickness formed, An In—Ti—Si—O film with a thickness of 60 nm was formed.
  • FIG. 4 shows the results obtained by depth resolution XPS measurement of the concentration distribution of Ti and Si elements in the fabricated In—Ti—Si—O film while Ar etching.
  • An In—Ti—Si—O film having a high Ti concentration, a low Si concentration, and a reverse concentration gradient in the central portion was formed on the side close to the gate insulating film 24 and the source / drain electrode 26/27 side.
  • the Id—Vg characteristics after an evaluation environment of 25 ° C. and light irradiation for 1000 seconds were measured.
  • FIG. 7 also shows the Id—Vg characteristics of an In—Ti—O thin film transistor. It can be seen that by irradiation with light having a wavelength of 420 to 600 nm, the I-off value of In—Ti—O increases and the threshold voltage also shifts to the negative side. On the other hand, the In—Si—O—N thin film transistor had almost the same characteristics after light irradiation as before light irradiation, and hardly deteriorated. Note that the Id-Vg characteristics of the In—Si—O—N thin film transistor and the In—Ti—O thin film transistor before light irradiation were substantially the same as those indicated by the broken line in FIG.
  • IGZO In—Ga—Zn—O
  • the thin film transistor using IGZO has a large threshold voltage shift of about 2 V due to light irradiation, and the electron mobility is as small as 5 cm 2 / Vs.
  • the thin film transistor using In—Ti—Si—O of Example A1 showed a high threshold voltage shift smaller than 1 V and an electron mobility close to 10 cm 2 / Vs.
  • the thin film transistor using In—Ti—Si—O of Example A1 has low contact resistance at the interface between the source electrode 26 / drain electrode 27 and the semiconductor layer 25, and has excellent gate controllability. It was.
  • Example B1 In this example corresponding to the first embodiment, the thin film transistor shown in FIG. 10 was manufactured and the operation was confirmed.
  • the thin film transistor shown in the figure has the same structure as that of the thin film transistor 201 shown in FIG. 8, and uses a Si layer 211 doped with a large amount of p-type impurities in place of the gate electrode 203 included in the thin film transistor 201 shown in FIG. It has become.
  • the thin film transistor of the example uses a Si substrate doped with a p-type impurity, forms the insulator layer 204 by oxidizing the surface, and then forms the semiconductor layer 205 on the surface of the insulator layer 204 using a method described later. It was manufactured by doing.
  • the source electrode 208 and the drain electrode 209 were formed by mask vapor deposition on the surface of the semiconductor layer 205.
  • the source electrode 208 and the drain electrode 209 are made of gold (Au) and have a thickness of 50 nm. Further, the separation distance (gate length) between the source electrode 208 and the drain electrode 209 was 350 ⁇ m, and the length of the facing portion was 940 ⁇ m.
  • the semiconductor layer 205 was formed by a sputtering method (DC sputtering) using a sputtering apparatus and using a Sn—W—O target as a target material under the following sputtering conditions.
  • a Sn—W—O target a 20% W-added Sn-based sample product was used.
  • the thickness of the deposited semiconductor layer 205 was 20 nm.
  • FIG. 11 shows the measurement results of the transfer characteristics of this thin film transistor.
  • FIG. 12 shows the electrical conduction characteristics of Sn—O and Sn—W—O thin film transistors when the ratio of O 2 / (Ar + O 2 ) is changed in the range of 5 to 25% under the above sputtering conditions.
  • Sn—W—O exhibits superior electrical conductivity compared to Sn—O at all oxygen ratios in FIG. This is suitable from tin oxide (Sn—O) with high accuracy because the oxygen dissociation energy of W—O bond (720 ⁇ 71 kJ / mol) is larger than that of Sn—O (528 kJ / mol). This is the effect of controlling the amount of oxygen deficiency by desorbing oxygen.
  • Sn—W—O indicates that the change in electrical conduction characteristics is smaller than the change in the ratio of O 2 / (Ar + O 2 ). From this result, it can be seen that Sn—W—O has a larger process margin.
  • the semiconductor layer 205 was formed by a sputtering method (DC sputtering) using a sputtering apparatus and using a Sn—W—Yb—O target as a target material under the following sputtering conditions.
  • Sn—W—O target 20% W and 2% Yb-added Sn-based sample products were used.
  • the thickness of the deposited semiconductor layer 205 was 20 nm.
  • FIG. 14 shows the results of measuring the characteristics of the thin film transistor of the fourth invention.
  • Example C the fifth invention of the present application will be described by Example C, but the fifth invention of the present application is not limited to these Examples.
  • Example C the thin film transistor 400 shown in FIG. 16 was manufactured and the operation was confirmed.
  • a substrate 450 that is a Si layer doped with a large amount of p-type impurities is used as the gate electrode instead of the gate electrode 330 shown in FIG.
  • the thin film transistor of Example C uses a Si substrate 450 doped with a p-type impurity, forms an insulator layer 410 by oxidizing the surface, and then forms an oxide semiconductor on the surface of the insulator layer 410 using a method described later.
  • the semiconductor layer 420 was formed.
  • the source electrode 430 and the drain electrode 440 were formed by mask vapor deposition on the surface of the semiconductor layer 420 of an oxide semiconductor.
  • the source electrode 430 and the drain electrode 440 are made of gold (Au) and have a thickness of 50 nm. Further, the distance (gate length) between the source electrode 430 and the drain electrode 440 was 350 ⁇ m, and the length of the facing portion was 940 ⁇ m.
  • an oxide semiconductor layer 420 was fabricated as follows.
  • FIG. 17 shows the results of In3d XPS spectra of the In—Si—O film before and after the heat treatment at 150 ° C.
  • FIG. 17 shows the results of In3d XPS spectra of the In—Si—O film before and after the heat treatment at 150 ° C.
  • (a) is an In3dXPS spectrum of an In—Si—O semiconductor before the heat treatment
  • (b) is an In3dXPS spectrum of an In—Si—O semiconductor having an In—OH bond after the heat treatment.
  • the peak position due to the In—OH bond in the In—Si—O semiconductor into which the —OH group was introduced after the heat treatment was found at 444 eV, and the In—Si—O semiconductor before the heat treatment was observed.
  • the peak position due to the In—O bond in is observed at 443.5 eV.
  • the peak position due to the In—OH bond in the In—Si—O semiconductor into which the —OH group is introduced after the heat treatment is the peak position due to the In—O bond in the In—Si—O semiconductor before the heat treatment.
  • the content of OH groups to be introduced is preferably 0.1% or more and 10% or less. If it becomes 10% or less, it is possible to avoid a source of mobile ions (herein, “mobile ions” means ions localized in the oxide corresponding to the application of positive and negative voltages). This is because the metal behavior can be prevented from being more than the property of the semiconductor.
  • FIG. 18 shows the result of showing the I d -V g characteristics after irradiation with light having a wavelength of 420 nm or more and 600 nm or less for 100 seconds.
  • FIG. 18A shows the I d -V g characteristics of an In—Si—O semiconductor into which OH groups have not been introduced before light irradiation and an In—Si—O semiconductor having an In—OH bond before light irradiation.
  • (B) shows the I d -V g characteristics of an In—Si—O semiconductor having an In—OH bond after light irradiation
  • (c) shows an In group in which no OH group has been introduced after light irradiation.
  • the I d -V g characteristic of the —Si—O semiconductor is shown. As shown in FIG. 18, the I d -V g characteristics of the thin film transistor using the In—Si—O semiconductor having In—OH bonds before and after the light irradiation were almost the same. On the other hand, the I d -V g characteristics before and after the light irradiation of the thin film transistor using an In—Si—O semiconductor into which no OH group is introduced show that the I d curve shifts to the negative side compared to before the light irradiation, and is off. The current (I off ) value also tended to increase.
  • a thin film transistor using an In—Si—O semiconductor into which no OH group has been introduced cannot sufficiently suppress “threshold voltage shift” with respect to light irradiation having a wavelength of 420 nm to 600 nm. It was found that the “threshold voltage shift” can be sufficiently suppressed by introducing a group.
  • characteristic deterioration such as shift of threshold current due to light irradiation is suppressed, contact resistance at the interface between the source electrode and / or drain electrode and the semiconductor layer is low, and electron mobility is low. It is possible to provide thin film transistors that have high practical value, such as high gate control, and can be used in various industrial fields including liquid crystal displays and organic EL displays. Have sex.
  • the present invention can be applied to a semiconductor device such as a semiconductor element such as a thin film transistor and an electronic device such as an organic EL display or a liquid crystal display for which improvement in reliability with respect to light irradiation from a layer is desired.

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  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne : un transistor en couches minces qui présente un bon équilibre entre une suppression de détérioration des caractéristiques due à une exposition à un rayonnement de lumière et une faible résistance de contact ainsi qu'une excellente aptitude de régulation de grille ; et un procédé de fabrication du transistor en couches minces. Le problème peut être résolu au moyen dudit transistor en couches minces qui comprend une électrode source, une électrode déversoir, une couche semi-conductrice qui est prévue de sorte à se trouver en contact avec l'électrode source et l'électrode déversoir, une électrode grille qui est prévue de sorte à correspondre à un canal entre l'électrode source et l'électrode déversoir, et une couche d'isolant qui est prévue entre l'électrode grille et la couche semi-conductrice, et qui est caractérisé en ce que : la couche semi-conductrice est constituée d'un oxyde métallique composite qui est obtenu par addition, à un premier oxyde métallique pouvant générer des porteurs d'électrons au moyen de l'introduction de déficits en oxygène, d'un second oxyde qui présente une énergie de dissociation de l'oxygène qui est supérieure à l'énergie de dissociation de l'oxygène du premier oxyde métallique dans une proportion supérieure ou égale à 200 kJ/mol ; et la concentration d'un élément spécifique parmi les éléments constituant le second oxyde présente la valeur maximale ou la valeur minimale dans la partie centrale de la couche semi-conductrice dans la direction de l'épaisseur.
PCT/JP2015/051845 2014-01-31 2015-01-23 Transistor en couches minces, semi-conducteur à base d'oxyde et son procédé de production Ceased WO2015115330A1 (fr)

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JP2014016273A JP6252903B2 (ja) 2014-01-31 2014-01-31 薄膜トランジスタおよびその製造方法
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JP2014016631A JP6252904B2 (ja) 2014-01-31 2014-01-31 酸化物半導体およびその製法
JP2014-016273 2014-01-31
JP2014-016630 2014-01-31
JP2014016630A JP6261125B2 (ja) 2014-01-31 2014-01-31 酸化物薄膜トランジスタおよびその製造方法

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