WO2011040028A1 - In-Ga-Zn-O系酸化物焼結体 - Google Patents
In-Ga-Zn-O系酸化物焼結体 Download PDFInfo
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- WO2011040028A1 WO2011040028A1 PCT/JP2010/005885 JP2010005885W WO2011040028A1 WO 2011040028 A1 WO2011040028 A1 WO 2011040028A1 JP 2010005885 W JP2010005885 W JP 2010005885W WO 2011040028 A1 WO2011040028 A1 WO 2011040028A1
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Definitions
- the present invention relates to an oxide sintered body.
- the present invention relates to an oxide sintered body suitable for forming an amorphous oxide film by sputtering.
- TFTs thin film transistors
- LCD liquid crystal display devices
- EL electroluminescence display devices
- FED field emission displays
- a silicon semiconductor compound As a material for a semiconductor layer (channel layer) which is a main member of a field effect transistor, a silicon semiconductor compound is most widely used.
- a silicon single crystal is used for a high-frequency amplifying element or an integrated circuit element that requires high-speed operation.
- an amorphous silicon semiconductor (amorphous silicon) is used for a liquid crystal driving element or the like because of a demand for a large area.
- an amorphous silicon thin film can be formed at a relatively low temperature, its switching speed is slower than that of a crystalline one, so when used as a switching element to drive a display device, it may not be able to follow the display of high-speed movies. is there.
- amorphous silicon having a mobility of 0.5 to 1 cm 2 / Vs could be used, but when the resolution is SXGA, UXGA, QXGA or higher, 2 cm 2 / Mobility greater than Vs is required. Further, when the driving frequency is increased in order to improve the image quality, higher mobility is required.
- the crystalline silicon-based thin film has a high mobility
- problems such as requiring a large amount of energy and the number of processes for manufacturing, and a problem that it is difficult to increase the area.
- laser annealing using a high temperature of 800 ° C. or higher and expensive equipment is necessary.
- a crystalline silicon-based thin film is difficult to reduce costs such as a reduction in the number of masks because the element configuration of a TFT is usually limited to a top gate configuration.
- an amorphous oxide semiconductor thin film is produced by sputtering using a target (sputtering target) made of an oxide sintered body.
- a target made of a compound having a homologous crystal structure represented by the general formula In 2 Ga 2 ZnO 7-d InGaZnO 4 is disclosed (Patent Documents 1, 2, and 3).
- Patent Documents 1, 2, and 3 a target made of a compound having a homologous crystal structure represented by the general formula In 2 Ga 2 ZnO 7-d InGaZnO 4 is disclosed (Patent Documents 1, 2, and 3).
- sintering density relative density
- Non-Patent Document 1 each of In 2 Ga 2 ZnO 7 , ZnGa 2 O 4, and ZnO using a sintered body containing indium oxide, zinc oxide, and gallium oxide synthesized by reaction in a platinum tube. Studies on phase relationships have been disclosed. However, the production method and properties as an oxide sintered body, and the crystal type and target properties suitable as a sputtering target for producing an oxide semiconductor have not been studied.
- Non-Patent Document 1 For an oxide composed of a compound having a bixbite structure represented by In 2 O 3 and a compound having a spinel structure represented by ZnGa 2 O 4 , (InGaO 3 ) 2 ZnO powder is used for a long time (12 It is known that there are cases where it is decomposed and obtained as a powder when it is overheated (Non-Patent Document 1), or when InGaZnO 4 is heat-treated in a reducing atmosphere and obtained as a powder (Non-Patent Document 2). It was done. However, examination of physical properties and methods for producing oxide sintered bodies have not been studied.
- Oxids doped with In 2 O 3 in the ZnGa 2 O 4 is being considered as a phosphor, a small content of compounds showing bixbyite structure represented by In 2 O 3, those having a high resistance Met. Therefore, it has not been studied as an oxide sintered body or a sputtering target (Non-patent Document 3).
- JP-A-8-245220 JP 2007-73312 A International Publication No. 2009/084537 International Publication No. 2008/072486
- An object of the present invention is to obtain an oxide sintered body for forming an oxide semiconductor film having a low resistivity, a high relative density, a high bending strength, and good reproducibility of film formation.
- the sputtering target made of a compound having a homologous crystal structure represented by the general formula In 2 Ga 2 ZnO 7-d or InGaZnO 4 has a problem in the manufacturing process and film formability.
- the present invention has found that no reduction treatment at a high temperature for reducing the resistance is required and that the film formation is excellent in stability and reproducibility, and the present invention has been completed.
- the following oxide sintered bodies and the like are provided. 1.
- In In (indium element), Ga (gallium element) and Zn (zinc element),
- the total content of In, Ga and Zn with respect to all elements excluding oxygen element is 95 atomic% or more, Comprising a compound showing a bixbyite structure represented by In 2 O 3, and a compound showing a spinel structure represented by ZnGa 2 O 4, the oxide sintered body.
- the atomic ratio of Ga to the total of In, Ga and Zn satisfies the following formula (1), 2.
- the oxide sintered body according to 1, wherein an atomic ratio of Zn to a total of In, Ga and Zn satisfies the following formula (2).
- One of the compound having a bixbite structure represented by In 2 O 3 and the compound having a spinel structure represented by ZnGa 2 O 4 is a first component (main component), and the other is a second component.
- a compound having a bixbite structure represented by In 2 O 3 has a maximum peak intensity (I (In 2 O 3 )) in X-ray diffraction (XRD) and a spinel structure represented by ZnGa 2 O 4.
- the ratio (I (ZnGa 2 O 4 ) / I (In 2 O 3 )) of the maximum peak intensity (I (ZnGa 2 O 4 )) of the compound shown is from 1 to 3, which is 0.80 or more and 1.25 or less
- X is at least one selected from the group consisting of Sn, Ge, Zr, Hf, Ti, Si, Mo, and W.
- a sputtering target comprising the oxide sintered body according to any one of 10.1 to 9. 11.
- the oxide sintered body according to any one of 1 to 9, comprising a step of sintering a molded body made of a raw material containing indium oxide powder, gallium oxide powder and zinc oxide powder at 1160 to 1380 ° C. for 1 to 80 hours. Manufacturing method.
- 12 The method for producing an oxide sintered body according to 11, wherein the oxygen pressure in the sintering step is 1 to 3 atm.
- an oxide sintered body having a low resistivity, a high relative density, and a high bending strength can be provided.
- FIG. 2 is an X-ray diffraction chart of a sintered body produced in Example 1.
- FIG. 3 is an X-ray diffraction chart of a sintered body produced in Example 2.
- FIG. 3 is an X-ray diffraction chart of a sintered body produced in Comparative Example 1.
- 6 is an X-ray diffraction chart of a sintered body produced in Comparative Example 2.
- 6 is a photograph of black spots observed on a target surface prepared in Comparative Example 3.
- the oxide sintered body of the present invention is characterized by comprising an oxide sintered body containing In (indium element), Ga (gallium element) and Zn (zinc element). And the total content rate of In, Ga, and Zn with respect to all the elements of the oxide sintered compact except an oxygen element is 95 atomic% or more. If the content is less than 95 atomic%, the relative density of the oxide sintered body may decrease, or the mobility may decrease when a thin film transistor is manufactured. The total content is preferably 99 atomic% or more.
- the atomic ratio of each element contained in the oxide sinter can be determined by quantitative analysis of the contained elements using an inductively coupled plasma emission spectrometer (ICP-AES). Specifically, in the analysis using ICP-AES, when a solution sample is atomized with a nebulizer and introduced into an argon plasma (about 6000 to 8000 ° C.), the elements in the sample are excited by absorbing thermal energy. , Orbital electrons move from the ground state to high energy level orbitals. These orbital electrons move to a lower energy level orbit in about 10 ⁇ 7 to 10 ⁇ 8 seconds. At this time, the energy difference is emitted as light to emit light.
- ICP-AES inductively coupled plasma emission spectrometer
- this light shows a wavelength (spectral line) unique to the element
- the presence of the element can be confirmed by the presence or absence of the spectral line (qualitative analysis).
- the magnitude (luminescence intensity) of each spectral line is proportional to the number of elements in the sample
- the sample concentration can be obtained by comparing with a standard solution having a known concentration (quantitative analysis). After identifying the elements contained in the qualitative analysis, the content is obtained by qualitative analysis, and the atomic ratio of each element is obtained from the result.
- the oxide sintered body of the present invention is an oxide sintered body containing a compound having a bixbite structure represented by In 2 O 3 and a compound having a spinel structure represented by ZnGa 2 O 4. It is characterized by becoming. Thereby, an oxide sintered body having a low resistivity, a high relative density, and a high bending strength can be obtained.
- the “Bixbite structure represented by In 2 O 3 ” (rare earth oxide C-type crystal structure) is a cubic system having a space group of (T h 7 , I a3 ), It is also called Mn 2 O 3 (I) type oxide crystal structure.
- the crystal structure of the bixbite structure represented by In 2 O 3 is one of the crystal structures of the compound represented by MX 2 (M: cation, X: anion) From the fluorite crystal structure, one out of every four anions is missing. The anion (usually oxygen in the case of an oxide) is coordinated to the cation, and the remaining two anion sites are empty (the empty anion sites are both quasi-ion sites). (Refer to "Technology of transparent conductive film").
- the crystal structure of the bixbyite structure represented by In 2 O 3 in which oxygen (anion) is coordinated to 6 positive ions (cations) has an oxygen octahedral ridge shared structure.
- the ns orbitals of the p metal which is a cation, overlap each other to form an electron conduction path, and the effective mass is reduced, so that high electron mobility is exhibited. Furthermore, the crystal structure of the bixbite structure represented by In 2 O 3 tends to generate oxygen vacancies. Accordingly, oxygen deficiency can be generated in the crystal structure of the bixbite structure represented by In 2 O 3 to reduce resistance without performing reduction treatment.
- the crystal structure of the bixbite structure represented by In 2 O 3 is JCPDS card no. If the 6-0416 pattern is shown, the stoichiometric ratio may deviate from M 2 X 3 . That is, it may be M 2 O 3-d .
- the oxygen deficiency d is preferably in the range of 3 ⁇ 10 ⁇ 5 to 3 ⁇ 10 ⁇ 1 . d can be adjusted by sintering conditions, atmosphere during sintering, temperature rise, temperature drop, or the like. Moreover, it can also adjust by performing a reduction process or an oxidation process after sintering.
- the amount of oxygen deficiency is a value obtained by subtracting the number of oxygen ions contained in one mole of oxide crystal from the number of stoichiometric amounts of oxygen ions in mole units.
- the number of oxygen ions contained in the oxide crystal can be calculated, for example, by measuring the amount of carbon dioxide produced by heating the oxide crystal in carbon powder using an infrared absorption spectrum.
- the number of stoichiometric oxygen ions can be calculated from the mass of the oxide crystal.
- a compound having a spinel structure represented by ZnGa 2 O 4 refers to JCPDS card No. 1 in X-ray diffraction.
- a compound showing the pattern of 38-1240 is meant.
- the crystal structure represented by ZnGa 2 O 4 is the JCPDS card no.
- the stoichiometric ratio may be shifted. That is, it may be ZnGa 2 O 4-d .
- the oxygen deficiency d is preferably in the range of 3 ⁇ 10 ⁇ 5 to 3 ⁇ 10 ⁇ 1 .
- d can be adjusted by sintering conditions, atmosphere during sintering, temperature rise, temperature drop, or the like. Moreover, it can also adjust by performing a reduction process or an oxidation process after sintering.
- the atomic ratio of Ga to the total of In, Ga and Zn satisfies the following formula (1), and the atomic ratio of Zn to the total satisfies the following formula (2).
- the atomic ratio of Zn to the total satisfies the following formula (2). preferable. 0.20 ⁇ Ga / (In + Ga + Zn) ⁇ 0.49 (1) 0.10 ⁇ Zn / (In + Ga + Zn) ⁇ 0.30 (2)
- the atomic ratio of Ga is more than 0.20 in the above formula (1), a sintered body containing the compound having the spinel structure represented by ZnGa 2 O 4 described above can be easily obtained. Moreover, when the thin film obtained is used for a thin film transistor (TFT), uniformity and reproducibility of TFT characteristics can be improved. On the other hand, when the atomic ratio of Ga is less than 0.49, the density of the oxide sintered body can be easily increased and the resistance can be easily decreased.
- the atomic ratio [Ga / (In + Ga + Zn)] of Ga is preferably 0.25 or more and 0.48 or less, more preferably 0.35 or more and 0.45 or less, and particularly 0.37 or more and 0. .43 or less is preferable.
- the atomic ratio of Zn exceeds 0.10, the density of the oxide sintered body can be easily increased and the resistance can be easily decreased. In addition, since the crystallization temperature is increased, the amorphous state of the film is stabilized when the amorphous oxide semiconductor film is manufactured. When the atomic ratio of Zn exceeds 0.10, microcrystals are hardly generated in the amorphous oxide semiconductor film. Further, it is difficult for residues to remain when wet etching is performed. On the other hand, when the atomic ratio of Zn is less than 0.30, it becomes easy to obtain a sintered body including the above-described crystal type. Moreover, the uniformity and reproducibility of TFT characteristics can be improved by using the obtained thin film.
- the atomic ratio [Zn / (In + Ga + Zn)] of Zn is preferably 0.15 or more and 0.25 or less, and more preferably 0.17 or more and 0.23 or less.
- the In atomic ratio [In / (In + Ga + Zn)] is preferably greater than 0.20 and less than 0.55.
- the atomic ratio of In exceeds 0.20, it becomes easy to obtain a sintered body including the above-described crystal type. Moreover, the uniformity and reproducibility of TFT characteristics can be improved by using the obtained thin film.
- the atomic ratio of In is less than 0.55, the density of the oxide sintered body can be easily increased and the resistance can be easily decreased.
- the atomic ratio [In / (In + Ga + Zn)] of In is preferably 0.25 or more and 0.50 or less, more preferably 0.35 or more and 0.45 or less, and particularly 0.37 or more and 0. .43 or less is preferable.
- An oxide sintered body satisfying the above range has a smaller In content than ITO or the like. Therefore, nodule generation at the time of sputtering is extremely small as compared with a target containing a large amount of In such as ITO. In addition, when the thin film transistor is manufactured, yield reduction due to particles generated from abnormal discharge due to nodules is small.
- the atomic ratio [In / (In + Ga)] of In to the total of In and Ga is preferably 0.59 or less.
- any one of the compound showing the bixbite structure represented by In 2 O 3 and the compound showing the spinel structure represented by ZnGa 2 O 4 is the first. It is preferable that it is a component (main component) and the other is a second component (subcomponent).
- the effects of the present invention (reduction in resistivity of the sintered body, improvement in TFT mobility, uniformity in TFT characteristics, reproducibility, etc.) can be further enhanced. It can be easily expressed.
- the maximum peak of the X-ray diffraction of each component is a main component or a subcomponent. Specifically, the height of the maximum peak of X-ray diffraction of each component is compared, and the highest component is the first component and the second highest component is the second component. The same applies to the third and subsequent components.
- the maximum peak height of the X-ray diffraction of the compound having the crystal structure represented by ⁇ -Ga 2 O 3 exhibits the above-described bixbite structure represented by In 2 O 3.
- the maximum peak height of the compound is preferably 1/2 or less, more preferably 1/10 or less, and particularly preferably not confirmed by X-ray diffraction (in the case of 1/100 or less X-ray diffraction) ).
- a smaller amount of the compound having a crystal structure represented by ⁇ -Ga 2 O 3 can suppress an increase in target resistance and occurrence of abnormal discharge.
- the maximum peak height of the X-ray diffraction of the compound showing the homologous crystal structure represented by In 2 Ga 2 ZnO 7 or InGaZnO 4 is the same as that of the compound showing the crystal structure represented by In 2 O 3 described above. It is preferably less than or equal to one-half of the maximum peak height, more preferably less than or equal to one-tenth, and particularly preferably not confirmed by X-ray diffraction. For example, when it is 1/100 or less of the maximum peak of X-ray diffraction of a compound having a crystal structure represented by In 2 O 3 , it cannot be confirmed by X-ray diffraction. If there are many compounds showing a homologous crystal structure, problems such as the need for a reduction treatment may appear when sintering in an oxidizing atmosphere.
- the compounds showing bixbyite structure represented by an In 2 O 3 a maximum peak intensity in X-ray diffraction (XRD) (I (In 2 O 3)), a spinel structure represented by ZnGa 2 O 4
- the ratio (I (ZnGa 2 O 4 ) / I (In 2 O 3 )) of the maximum peak intensity (I (ZnGa 2 O 4 )) of the compound shown is preferably 0.80 or more and 1.25 or less. That the maximum peak intensity ratio is in the above range means that the sputtering target contains substantially the same amount of a compound having a bixbite structure represented by In 2 O 3 and a spinel structure represented by ZnGa 2 O 4. .
- the maximum peak intensity ratio is more preferably 0.90 or more and 1.10 or less, and particularly preferably 0.95 or more and 1.05 or less. More preferably, it is 0.99 or more and 1.05 or less.
- the maximum peak intensity in X-ray diffraction means the peak height of the highest peak (sometimes called a main peak). The attribution of the peak is judged by comparing with the pattern of the JCPDS card. If the patterns match, the peak may be shifted.
- the maximum peak intensity of the compound showing the bixbyite structure represented by 2 O 3 is usually close to 30 ⁇ 31 °, the compounds exhibiting a spinel structure represented by ZnGa 2 O 4
- the maximum peak intensity is usually confirmed around 35 to 36 °.
- difference of a peak position shows the change of a lattice constant (a), and it is preferable that a is 10.05 or more and less than 10.10.
- a is 10.05 or more and less than 10.10, it can be expected that the distance between atoms is shortened and the mobility is improved.
- a is less than 10.05, the distortion of the structure is increased, the target property is lost, and the mobility may be reduced due to scattering.
- the maximum peak can be calculated from other peaks. Specifically, the maximum peak can be obtained by back-calculating peak intensities other than the maximum peak using intensity ratio data published in ICDD (International Center for Diffraction Data).
- the oxide sintered body of the present invention is preferably composed of a composite oxide containing In, Ga, and Zn having an In-rich phase and a Ga-rich phase. Further, those in which continuity is seen in the In-rich phase are preferable, and it is particularly preferable that the In-rich phase (sea) has a sea-island structure in which a Ga-rich phase (island) exists.
- the In-rich phase has a sea-island structure in which a Ga-rich phase (island) exists.
- the In rich phase means a phase having a larger indium content than the surroundings.
- the Ga-rich phase means a phase having a higher gallium content than the surroundings.
- the In rich phase or Ga rich phase can be confirmed by an X-ray microanalyzer (EPMA).
- the average particle size of each phase is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m or less, particularly preferably 20 ⁇ m or less because sputtering is stable. There is no lower limit to the particle size of each phase, but it is usually 0.1 ⁇ m or more.
- the In-rich phase preferably has a lower oxygen content than the surrounding phase. It can be confirmed by EPMA that the oxygen content of the In-rich phase is lower than that of the surrounding phase.
- an oxide sintered body having a relative density of 90% or more, a resistivity measured by a four-probe method of 50 m ⁇ cm or less, and the number of black spots on the surface of 0.1 piece / cm 2 or less can be obtained.
- the relative density is more preferably 95% or more, further preferably 98% or more, and particularly preferably 99% or more.
- the relative density is a density calculated relative to the theoretical density calculated from the weighted average. The density calculated from the weighted average of the density of each raw material is the theoretical density, which is defined as 100%.
- the resistivity of the oxide sintered body is 50 m ⁇ cm or less, the target is less likely to crack during sputtering, and the continuous stability of sputtering is improved and abnormal discharge is reduced.
- the resistivity is preferably 30 m ⁇ cm or less, more preferably 20 m ⁇ cm or less, and even more preferably 10 m ⁇ cm or less.
- the resistivity is a value measured by a four-probe method using a resistivity meter.
- the number of black spots on the surface of the oxide sintered body is more than 0.1 / cm 2 , particles may be generated during sputtering, nodules may be generated, or abnormal discharge may increase. When these phenomena occur, there is a risk that the yield, reproducibility, and uniformity of the TFT are lowered when the TFT is manufactured.
- the number of black spots is more preferably 0.01 piece / cm 2 or less, and further preferably 0.001 piece / cm 2 or less.
- the number of black spots on the surface is obtained by dividing the number of black spots visually counted under daylight in the north window by the total area observed.
- the oxide sintered body of the present invention preferably further contains a positive tetravalent element X, and the atomic ratio of X with respect to the sum of In, Ga, Zn and X satisfies the following formula (3). 0.0001 ⁇ X / (In + Ga + Zn + X) ⁇ 0.05 (3) If the atomic ratio of X exceeds 0.0001, the effect of adding the positive tetravalent element X is exhibited, and an improvement in the relative density of the oxide sintered body and a reduction in resistance can be expected. Preferably, it is 0.0003 or more, particularly preferably 0.0005 or more.
- the atomic ratio of X is less than 0.05, a compound having a bixbite structure represented by In 2 O 3 and a spinel structure represented by ZnGa 2 O 4 are easily obtained, and the characteristics of the present invention are obtained. It is easy to be done. Preferably, it is 0.04 or less, and particularly preferably 0.03 or less.
- X By adding X, when a thin film transistor is formed, a lower oxide of a positive tetravalent element is generated, and the possibility that the transistor characteristics are deteriorated is reduced. In addition, there is little occurrence of unevenness in characteristics due to the structure changing in the thickness direction of the target.
- the atomic ratio of X is 0.05 or more, the generation of the lower oxide of X becomes excessive, and the resistance of the oxide sintered body may be increased. In addition, mobility may decrease when a transistor is manufactured.
- a positive tetravalent element is an element which can take a positive tetravalent.
- the positive tetravalent element X, Sn, Ge, Si, C, Pb, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Ir, Pd, Pt , Ce, Pr, Tb, Se, Te and the like.
- Sn, Ge, Si, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, and Ce are preferable, and Sn, Ge, Si, Ti, Zr, and Hf are more preferable, Sn, Ge, Si, and Zr are more preferable, and Sn is particularly preferable.
- Sn, Ge, Si, and Zr are preferable, Sn and Zr are more preferable, and Sn is particularly preferable.
- X is preferably at least one selected from the group consisting of Sn, Ge, Zr, Hf, Ti, Si, Mo, and W.
- the present invention preferably contains a Sn element in the crystal structure of the compound showing the bixbyite structure represented by In 2 O 3.
- a Sn element in the crystal structure of the compound showing the bixbyite structure represented by In 2 O 3.
- the effect that the resistivity of oxide sinter is easy to fall is acquired.
- the inclusion of Sn in the crystal structure represented by In 2 O 3 can be confirmed by EPMA measurement.
- the number of aggregated particles of tin oxide having a diameter of 10 ⁇ m or more is preferably 2.5 or less per 1.00 mm 2 . Thereby, the abnormal discharge by the aggregation particle
- the metal element contained in the oxide sintered body may be substantially only In, Ga and Zn, or only In, Ga, Zn and X. Note that “substantially” means that no elements other than impurities, which are inevitably included due to raw materials, manufacturing processes, and the like are not included.
- the oxide sintered body of the present invention is, for example, a molded body made of a raw material containing indium oxide powder, gallium oxide powder, zinc oxide powder, and, if necessary, an oxide of a positive tetravalent element X or an oxide of another metal element. Is obtained by sintering at 1160 to 1380 ° C. for 1 to 80 hours. This will be specifically described below.
- the powder of each oxide as a raw material preferably has a specific surface area of 2 to 16 m 2 / g.
- the median diameter is preferably 0.1 to 3 ⁇ m.
- the purity of each raw material powder is usually 99.9% (3N) or higher, preferably 99.99% (4N) or higher, more preferably 99.995% or higher, particularly preferably 99.999% (5N) or higher. . If the purity of each raw material powder is less than 99.9% (3N), the semiconductor characteristics may be deteriorated due to impurities, appearance defects such as uneven color and spots may occur, and reliability may be reduced. is there.
- a composite oxide such as In—Zn oxide, In—Ga oxide, or Ga—Zn oxide may be used as a raw material.
- an In—Zn oxide or a Ga—Zn oxide is preferably used because Zn sublimation can be suppressed.
- the mixture of raw material powders is mixed and ground using, for example, a wet medium stirring mill.
- the specific surface area after pulverization is increased by 1.5 to 2.5 m 2 / g from the specific surface area of the raw material mixed powder, or is pulverized so that the average median diameter after pulverization is 0.6 to 1 ⁇ m. It is preferable to do.
- the increase in the specific surface area of the raw material mixed powder is less than 1.0 m 2 / g or the average median diameter of the raw material mixed powder after pulverization exceeds 1 ⁇ m, the sintered density may not be sufficiently increased.
- the increase in the specific surface area of the raw material mixed powder exceeds 3.0 m 2 / g, or if the average median diameter after pulverization is less than 0.6 ⁇ m, contamination from the pulverizer during pulverization (impurity contamination amount) ) May increase.
- the specific surface area of each powder is a value measured by the BET method.
- the median diameter of the particle size distribution of each powder is a value measured with a particle size distribution meter.
- the mixed powder When calcining, the mixed powder is held in an electric furnace or the like in an air atmosphere or an oxygen atmosphere at 800 to 1050 ° C. for about 1 to 24 hours. It is preferable to add and finely pulverize with a rotation speed of 50 to 1000 rpm and a rotation time of 1 to 10 hours.
- the obtained finely pulverized product has an average particle size (D50) of preferably 0.1 to 0.7 ⁇ m, more preferably 0.2 to 0.6 ⁇ m, and particularly preferably 0.3 to 0.55 ⁇ m or less. .
- the mixed powder obtained in the mixing and pulverizing step is dried with a spray dryer or the like and then molded.
- a known method such as pressure forming or cold isostatic pressing can be employed.
- Sintering is usually performed by heating at 1100 to 1380 ° C. for 1 to 100 hours. By setting it as 1100 degreeC or more, the relative density of oxide sinter improves and a resistivity falls easily. When the temperature is 1380 ° C. or lower, it is easy to prevent transpiration of zinc, and there is little risk that the composition of the sintered body changes or voids (voids) are generated in the sintered body due to transpiration. It also reduces the risk of damage to the furnace. By setting the sintering time to 1 hour or longer, variations due to insufficient sintering can be prevented. Moreover, the curvature and deformation
- the oxide sintered body including a compound having a crystal structure represented by In 2 O 3 and a compound having a crystal structure represented by ZnGa 2 O 4 , the oxide sintered body is manufactured at 1160 to 1380 ° C. at 1 to 80 Sintering is preferable, sintering at 1220 to 1340 ° C for 1.5 to 50 hours is more preferable, and sintering at 1220 to 1340 ° C for 2 to 20 hours is particularly preferable.
- the compact is heated at 700 to 900 ° C. for 0.5 to 8 hours before sintering and then sintered at the above temperature (two-stage sintering). Further, it is preferable that the temperature rise rate is less than 1 ° C./min up to 500 to 900 ° C., and then the temperature is switched to 1 ° C./min or more to raise the temperature to the above sintering temperature for sintering.
- Sintering is performed in the presence of oxygen.
- sintering is performed in an oxygen atmosphere by circulating oxygen, or sintering is performed under oxygen pressure.
- a preferable oxygen pressure is 0.5 to 5 atmospheres, and a more preferable oxygen pressure is 1 to 3 atmospheres.
- transpiration of zinc can be suppressed, and a sintered body free from voids (voids) can be obtained.
- the nitrogen content in the target can be reduced. Since the sintered body manufactured in this manner has a high density and generates less nodules and particles during use, an oxide semiconductor film having excellent film characteristics can be manufactured.
- the cooling rate after sintering is preferably 0.5 ° C./min or more, more preferably 2 ° C./min or more, and further preferably 3 ° C./min or more. If it is 0.5 ° C./min or more, it can be expected to suppress the precipitation of a stable crystal form at an intermediate temperature.
- the cooling rate after sintering is preferably 50 ° C./min or less. If it exceeds 50 ° C./min, it cannot be uniformly cooled and the properties may be uneven.
- a sputtering target can be produced by subjecting the oxide sintered body of the present invention obtained by the sintering step to a process such as polishing. Specifically, it is preferable to grind the sintered body with, for example, a surface grinder so that the surface roughness Ra is 5 ⁇ m or less. Further, the sputter surface of the target may be mirror-finished so that the average surface roughness Ra is 1000 angstroms or less.
- a surface grinder so that the surface roughness Ra is 5 ⁇ m or less.
- the sputter surface of the target may be mirror-finished so that the average surface roughness Ra is 1000 angstroms or less.
- known polishing techniques such as mechanical polishing, chemical polishing, and mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used.
- polishing to # 2000 or more with a fixed abrasive polisher polishing liquid: water
- lapping with loose abrasive lapping abrasive: SiC paste, etc.
- lapping by changing the abrasive to diamond paste can be obtained by:
- Such a polishing method is not particularly limited.
- cleaning, etc. can be used for the cleaning process of a target.
- cleaning, etc. can be used for the cleaning process of a target.
- ultrasonic cleaning and the like can also be performed.
- a method of performing multiple oscillation at a frequency of 25 to 300 KHz is effective.
- a reduction step after sintering is not necessary, but it may be performed in order to make the resistivity of the sintered body uniform as a whole.
- the reduction treatment include a method using a reducing gas, vacuum firing, or reduction using an inert gas.
- a reducing gas hydrogen, methane, carbon monoxide, a mixed gas of these gases and oxygen, or the like can be used.
- reduction treatment by firing in an inert gas nitrogen, argon, a mixed gas of these gases and oxygen, or the like can be used.
- the temperature during the reduction treatment is usually 100 to 800 ° C., preferably 200 to 800 ° C.
- the reduction treatment time is usually 0.01 to 10 hours, preferably 0.05 to 5 hours.
- the particle diameter of each compound in the oxide sintered body of the present invention is usually usually 200 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the particle size is an average particle size measured by EPMA. Although there is no lower limit to the particle size, it is usually 0.1 ⁇ m or more.
- the particle size for example, the mixing ratio of each oxide powder as the raw material, the particle size of the raw material powder, purity, heating time, sintering temperature, sintering time, sintering atmosphere, cooling time should be adjusted. Can be controlled. If the particle size of the compound is larger than 20 ⁇ m, nodules may be generated during sputtering. On the other hand, when the thickness is larger than 200 ⁇ m, unevenness is generated on the target surface, which tends to cause abnormal discharge during film formation.
- the bending strength of the sputtering target is preferably 8 kg / mm 2 or more, more preferably 10 kg / mm 2 or more, and particularly preferably 12 kg / mm 2 or more.
- the target is required to have a certain bending force because a load is applied during the transportation and mounting of the target and the target may be damaged.
- the bending strength is less than 8 kg / mm 2, there is a possibility that it cannot be used as a target.
- the bending strength of the target can be measured according to JIS R 1601.
- the range of variation of positive elements other than zinc in the target is preferably within 0.5%. Further, it is preferable that the range of density variation within the target is within 3%.
- the surface roughness Ra of the target is 0.5 ⁇ m or less, and it is preferable that the target has a non-directional ground surface. If Ra is larger than 0.5 ⁇ m or the polished surface has directivity, abnormal discharge may occur or particles may be generated.
- the number of pinholes having a ferret diameter of 2 ⁇ m or more in the target is preferably 50 / mm 2 or less per unit area, more preferably 20 / mm 2 or less, and even more preferably 5 / mm 2 or less.
- the ferret diameter means a parallel line interval in a certain direction sandwiching particles when the pinhole is regarded as particles. For example, it can be measured by observation with an SEM image at a magnification of 100 times.
- the oxide sintered body of the present invention preferably has a nitrogen content of 5 ppm (atoms) or less.
- the nitrogen content in the thin film decreases, and the reliability and uniformity of the TFT when the thin film is used as a thin film transistor (TFT). Can be improved.
- the nitrogen content of the oxide sintered body is more than 5 ppm, abnormal discharge during sputtering of the obtained target and the amount of adsorbed gas on the target surface may not be sufficiently suppressed, and nitrogen in the target Indium reacts during sputtering to generate black indium nitride (InN), which may be mixed into the semiconductor film and reduce the yield.
- InN indium nitride
- nitrogen atoms exceed 5 ppm, the nitrogen atoms become mobile ions and gather at the semiconductor interface due to gate voltage stress to generate traps, or nitrogen acts as a donor and degrades performance.
- a non-nitrogen atmosphere for example, an oxygen atmosphere
- sintering under oxygen inflow is more preferable because residual nitrogen is released.
- the nitrogen content in the sintered body can be measured with a trace total nitrogen analyzer (TN).
- the trace total nitrogen analyzer uses only nitrogen (N) or only nitrogen (N) and carbon (C) as the target elements in elemental analysis, and is used to determine the amount of nitrogen, or the amount of nitrogen and the amount of carbon.
- N nitrogen-containing inorganic substances or nitrogen-containing organic substances are decomposed in the presence of a catalyst, N is converted into nitrogen monoxide (NO), this NO gas is reacted with ozone in a gas phase, light is emitted by chemiluminescence, and the light emission. N is determined from the intensity.
- the obtained target can be bonded to a backing plate and mounted on various film forming apparatuses.
- the film forming method include a sputtering method, a PLD (pulse laser deposition) method, a vacuum deposition method, and an ion plating method.
- An amorphous oxide film can be obtained by forming a film using the target of the present invention. This film can be suitably used as a constituent member of a semiconductor element such as a thin film transistor.
- a semiconductor element such as a thin film transistor.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a thin film transistor.
- the thin film transistor 1 has a gate electrode 20 sandwiched between a substrate 10 and a gate insulating film 30, and a semiconductor film 40 is stacked on the gate insulating film 30 as an active layer (channel layer).
- An etch stopper 60 is formed on the semiconductor film 40.
- a source electrode 50 and a drain electrode 52 are provided so as to cover the vicinity of the end of the semiconductor film 40 and the vicinity of the end of the etch stopper 60.
- the film obtained by the sputtering target made of the oxide sintered body of the present invention can be used for the semiconductor film 40 of the thin film transistor 1.
- the film formation is performed by a film formation method such as sputtering using a sputtering target.
- the thin film transistor 1 in FIG. 1 is a so-called channel stopper type thin film transistor.
- the thin film transistor of the present invention is not limited to a channel stopper type thin film transistor, and an element configuration known in this technical field can be adopted.
- the etch stopper 60 of the thin film transistor 1 may not be formed.
- the members of the thin film transistor will be described.
- Substrate There is no particular limitation, and those known in this technical field can be used.
- glass substrates such as alkali silicate glass, non-alkali glass and quartz glass, silicon substrates, resin substrates such as acrylic, polycarbonate and polyethylene naphthalate (PEN), polymer film bases such as polyethylene terephthalate (PET) and polyamide Materials can be used.
- resin substrates such as acrylic, polycarbonate and polyethylene naphthalate (PEN)
- polymer film bases such as polyethylene terephthalate (PET) and polyamide Materials
- membrane obtained by the sputtering target which consists of oxide sinter of this invention is used.
- the semiconductor layer is preferably an amorphous film.
- adhesion characteristics with an insulating film and a protective layer can be improved, and uniform transistor characteristics can be easily obtained even in a large area.
- whether the semiconductor layer is an amorphous film can be confirmed by X-ray crystal structure analysis. The case where no clear peak is observed is amorphous.
- Protective layer The material for forming the protective layer is not particularly limited. What is generally used can be arbitrarily selected as long as the effects of the present invention are not lost. For example, SiO 2, SiNx, Al 2 O 3, Ta 2 O 5, TiO 2, MgO, ZrO 2, CeO 2, K 2 O, Li 2 O, Na 2 O, Rb 2 O, Sc 2 O 3, Y 2 O 3 , Hf 2 O 3 , CaHfO 3 , PbTi 3 , BaTa 2 O 6 , SrTiO 3 , AlN, or the like can be used.
- the number of oxygen in these oxides does not necessarily match the stoichiometric ratio (for example, it may be SiO 2 or SiO x).
- SiNx may contain a hydrogen element.
- the protective film may have a structure in which two or more different insulating films are stacked.
- Gate insulating film There is no restriction
- the number of oxygen in these oxides does not necessarily match the stoichiometric ratio (for example, it may be SiO 2 or SiO x).
- SiNx may contain a hydrogen element.
- the gate insulating film may have a structure in which two or more different insulating films are stacked.
- the gate insulating film may be crystalline, polycrystalline, or amorphous, but is preferably polycrystalline or amorphous that is easy to manufacture industrially.
- the gate insulating film may be an organic insulating film such as poly (4-vinylphenol) (PVP) or parylene. Further, the gate insulating film may have a stacked structure of two or more layers of an inorganic insulating film and an organic insulating film.
- PVP poly (4-vinylphenol)
- Electrode There are no particular limitations on the material for forming the gate electrode, the source electrode, and the drain electrode, and any commonly used material can be selected.
- transparent electrodes such as indium tin oxide (ITO), indium zinc oxide, ZnO, SnO 2 , metal electrodes such as Al, Ag, Cr, Ni, Mo, Au, Ti, Ta, Cu, or these An alloy metal electrode can be used.
- each component (layer) of the transistor can be formed by a method known in this technical field.
- a film formation method a chemical film formation method such as a spray method, a dip method, or a CVD method, or a physical film formation method such as a sputtering method, a vacuum evaporation method, an ion plating method, or a pulse laser deposition method.
- the method can be used. Since the carrier density is easily controlled and the film quality can be easily improved, a physical film formation method is preferably used, and a sputtering method is more preferably used because of high productivity.
- the formed film can be patterned by various etching methods.
- the semiconductor layer is formed by DC or AC sputtering using the target made of the oxide sintered body of the present invention.
- DC or AC sputtering damage during film formation can be reduced as compared with RF sputtering. For this reason, effects such as improvement in mobility can be expected in the field effect transistor.
- the heat treatment is preferably performed in an inert gas in an environment where the oxygen partial pressure is 10 ⁇ 3 Pa or less, or after the semiconductor layer is covered with a protective layer. Reproducibility is improved under the above conditions.
- mobility is preferably at least 1 cm 2 / Vs, more preferably at least 3 cm 2 / Vs, particularly preferably at least 8 cm 2 / Vs. If it is smaller than 1 cm 2 / Vs, the switching speed becomes slow, and there is a possibility that it cannot be used for a large-screen high-definition display.
- the on / off ratio is preferably 10 6 or more, more preferably 10 7 or more, and particularly preferably 10 8 or more.
- Example 1 [Production of oxide sintered body] As raw material powders, In 2 O 3 (specific surface area: 11 m 2 / g, purity 99.99%), Ga 2 O 3 (specific surface area: 11 m 2 / g, purity 99.99%) and ZnO (specific surface area: 9 m). 2 / g, purity 99.99%) was used. The raw materials were mixed so that the atomic composition ratio shown in Table 1 was obtained, and mixed for 4 minutes with a super mixer. Mixing was performed in the air at a rotational speed of 3000 rpm. The obtained mixed powder was calcined in an electric furnace at 1000 ° C. in an air atmosphere for about 5 hours.
- the obtained calcined powder was put into an attritor together with zirconia beads, and pulverized for 3 hours at 300 rpm.
- the raw material powder had an average particle diameter (D50) of 0.55 ⁇ m.
- Water was added to the finely pulverized raw material powder so as to form a slurry (sludge) having a solid content of 50% by weight. This slurry was granulated with a granulator.
- the inlet temperature of the apparatus was set to 200 ° C., and the outlet temperature was set to 120 ° C.
- the granulated powder of 450 kgf / cm 2 surface pressure after press-molded under the conditions of 60 seconds held in surface pressure of 1800kgf / cm 2 at hydrostatic pressure device (CIP), and molded and held for 90 seconds.
- the temperature was raised to 800 ° C. in an oxygen atmosphere (oxygen pressurization 2 atm) with a temperature rising rate of 0.5 ° C./minm and held at 800 ° C. for 5 hours.
- Table 1 shows the properties and physical properties of the sintered body. The evaluation was performed by the following method.
- Relative density (%) (density measured by Archimedes method) ⁇ (theoretical density) ⁇ 100
- Resistivity A resistivity meter (manufactured by Mitsubishi Chemical Co., Ltd., Loresta) was used for measurement based on the four-probe method (JIS R 1637), and the average value at 10 locations was defined as the resistivity.
- X-ray diffraction measurement (XRD) ⁇ Device: ULTIMA-III, manufactured by Rigaku Corporation -X-ray: Cu-K ⁇ ray (wavelength 1.5406mm, monochromatized with graphite monochromator) ⁇ 2 ⁇ - ⁇ reflection method, continuous scan (1.0 ° / min) ⁇ Sampling interval: 0.02 ° ⁇ Slit DS, SS: 2/3 °, RS: 0.6 mm
- FIG. 2-5 shows X-ray diffraction (XRD) data of the surfaces of the sintered bodies produced in Examples 1 and 2 and Comparative Examples 1 and 2.
- Example 2 and Comparative Examples 1 and 2 As shown in Table 1, a target and a TFT were prepared and evaluated in the same manner as in Example 1 except that the composition and the sintering conditions were changed. The results are shown in Table 1.
- Example 3 Production of oxide sintered body Specific surface area of 15 m 2 / g, purity of 99.99% In 2 O 3 powder, specific surface area of 14 m 2 / g, purity of 99.99% Ga 2 O 3 powder, and ratio ZnO powder having a surface area of 4 m 2 / g and a purity of 99.99% was blended and mixed and pulverized by a ball mill until the particle size of each raw material powder became 1 ⁇ m or less. The produced slurry was taken out and rapidly dried and granulated using a spray dryer under the conditions of a slurry supply rate of 140 ml / min, a hot air temperature of 140 ° C., and a hot air amount of 8 Nm 3 / min.
- the granulated product was molded at a pressure of 3 ton / cm 2 with a cold isostatic press to obtain a molded body.
- this compact was sintered.
- the temperature rise in the sintering is 1 ° C. while introducing oxygen gas at a flow rate of 10 L / min up to 600 to 800 ° C. after raising the temperature up to 600 ° C. in the air at a rate of 0.5 ° C./min.
- the temperature was increased at a rate of / min.
- the temperature was raised at a rate of 3 ° C./min in the temperature range of 800 to 1300 ° C.
- the oxygen pressurization was 2 atm.
- (B) Production of Sputtering Target A target sintered body is cut out from the sintered body produced above, the sides of the target sintered body are cut with a diamond cutter, and the surface is ground with a surface grinder.
- the target material was Ra 5 ⁇ m or less.
- the surface was air blown, and 12 types of frequencies were oscillated in 25 kHz increments between frequencies of 25 to 300 kHz, and ultrasonic cleaning was performed for 3 minutes. Thereafter, the target material was bonded to a backing plate made of oxygen-free copper with indium solder to obtain a target.
- the surface roughness Ra of this target was 0.5 ⁇ m or less, and had a ground surface with no directionality.
- the average crystal grain size of the sintered body was 10 ⁇ m or less.
- the number of pinholes having a ferret diameter of 2 ⁇ m or more inside the sintered body was 5 / mm 2 or less.
- the variation of the relative density in the plane direction of the target was 1% or less, and the average number of holes was 800 / mm 2 or less. Also, no sunspot was found.
- the variation in the relative density was obtained by cutting out 10 arbitrary locations of the sintered body, obtaining the density by the Archimedes method, and calculating from the following formula based on the average value, the maximum value, and the minimum value.
- Relative density variation (%) (maximum-minimum) / average x 100
- the average crystal grain size is determined by embedding the sintered body in a resin and polishing the surface with alumina particles having a grain size of 0.05 ⁇ m, and then using X-ray microanalyzer (EPMA) JXA-8621MX (JEOL Ltd.)
- EPMA X-ray microanalyzer
- the polished surface is magnified 5000 times using a product, and the maximum diameter of the crystal particles observed within a 30 ⁇ m ⁇ 30 ⁇ m square frame on the sintered body surface is measured. It was.
- the average number of pores is mirror-polished in any direction of the sintered body, etched, and the structure is observed with a SEM (scanning electron microscope) to count the number of pores with a diameter of 1 ⁇ m or more per unit area. It was.
- RF magnetron sputtering and DC magnetron sputtering were performed, and the sputtering state was evaluated.
- the obtained results are shown in Tables 4 and 5.
- the evaluation was performed by the following method.
- RF sputtering (1) Abnormal discharge The number of abnormal discharges generated per 3 hours was measured. The evaluation was A for 5 times or less, B for 6 to 10 times, C for 11 to 20 times, and D for 21 to 30 times.
- In-plane uniformity The ratio (maximum value / minimum value) of the maximum value and minimum value of specific resistance in the same plane was measured.
- FIG. 1 A channel stopper type thin film transistor (reverse stagger type thin film transistor) shown in FIG. 1 was produced.
- the substrate 10 a glass substrate (Corning 1737) was used.
- 10 nm thick Mo, 80 nm thick Al, and 10 nm thick Mo were laminated in this order on the substrate 10 by electron beam evaporation.
- a laminated film was formed on the gate electrode 20 by using a photolithography method and a lift-off method.
- a 200 nm thick SiO 2 film was formed on the gate electrode 20 and the substrate 10 by the TEOS-CVD method to form the gate insulating layer 30.
- the substrate temperature is 70 ° C.
- the deposited oxide semiconductor film and protective film were processed into appropriate sizes by a photolithography method and an etching method. After the formation of the etching stopper layer 60, Mo having a thickness of 5 nm, Al having a thickness of 50 nm, and Mo having a thickness of 5 nm were laminated in this order, and the source electrode 50 and the drain electrode 52 were formed by photolithography and dry etching. . After that, heat treatment was performed in the atmosphere at 300 ° C. for 60 minutes to manufacture a transistor with a channel length of 10 ⁇ m and a channel width of 100 ⁇ m. In the substrate (TFT panel), a total of 100 TFTs were arranged at equal intervals in 10 rows ⁇ 10 columns. The evaluation results of the target and the thin film transistor are shown in Table 2-5. The thin film transistor was evaluated as follows.
- Mobility (field effect mobility ( ⁇ )) and on / off ratio Measurement was performed using a semiconductor parameter analyzer (Keutley 4200) at room temperature in a light-shielded environment.
- the ratio (first batch / fifth batch) of the average field effect mobility of the first batch and the fifth batch in five continuous batches was measured.
- the ratio of average field effect mobility was classified and evaluated according to the following criteria. 1.10 or less: A, 1.20 or less: B, 1.50 or less: C, more than 1.50: D
- Example 4-21, Comparative Example 3-10 As shown in Tables 2 and 3, a target and a thin film transistor were prepared and evaluated in the same manner as in Example 3 except that the raw materials, composition, production conditions, and the like were changed. The results are shown in Table 2-5.
- As the tin oxide SNO06PB manufactured by Kojundo Chemical Laboratory Co., Ltd. was used.
- As an oxide of Ge GEO07PB manufactured by Kojundo Chemical Laboratory Co., Ltd. was used.
- As an oxide of Hf HFO01PB manufactured by Kojundo Chemical Laboratory Co., Ltd. was used.
- As the Ti oxide TIO14PB manufactured by Kojundo Chemical Laboratory Co., Ltd. was used.
- As an oxide of Si SIO14PB manufactured by Kojundo Chemical Laboratory Co., Ltd.
- Example 12 when the target of Example 12 was measured by EPMA, it was confirmed that the target had an In-rich phase and a Ga-rich phase. It was also confirmed that the In-rich layer had a lower oxygen content than the other layers. Further, it was confirmed that Sn was included in the crystal structure represented by In 2 O 3 . Further, the number of aggregated particles of tin oxide having a diameter of 10 ⁇ m or more in the sputtering target was 2.5 or less per 1.00 mm 2 .
- the surface areas of the oxides of the positive tetravalent element X used in Examples 10-19 are as follows. Tin oxide: 6m 2 / g Each oxide of Ge, Zr, Hf, Ti, Si: 10 m 2 / g Mo and W oxides: 8 m 2 / g
- FIG. (B) The photograph which observed the black spot of the target surface produced in the comparative example 3 is shown in FIG. (B) is an enlarged photograph of (a).
- Example 3 and Comparative Example 10 were visually compared for the amount of particles generated when DC sputtering was performed. After sputtering for 120 hours, the amount of particles deposited on the inner wall of the chamber of Comparative Example 10 was larger than that of Example 3.
- Example 3 a target and a thin film transistor were prepared and evaluated in the same manner as in Example 3 except that sintering was performed at 1400 ° C. for 2 hours in the atmosphere. The results are shown in Tables 6 and 7.
- the sputtering target of the present invention can be suitably used for forming an oxide semiconductor film.
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Abstract
Description
アモルファスシリコンの薄膜は、比較的低温で形成できるものの、結晶性のものに比べてスイッチング速度が遅いため、表示装置を駆動するスイッチング素子として使用したときに、高速な動画の表示に追従できない場合がある。具体的に、解像度がVGAである液晶テレビでは、移動度が0.5~1cm2/Vsのアモルファスシリコンが使用可能であったが、解像度がSXGA、UXGA、QXGAあるいはそれ以上になると2cm2/Vs以上の移動度が要求される。また、画質を向上させるため駆動周波数を上げるとさらに高い移動度が必要となる。
例えば、一般式In2Ga2ZnO7-dInGaZnO4で表されるホモロガス結晶構造を示す化合物からなるターゲットが公開されている(特許文献1、2、3)。しかしながら、このターゲットでは焼結密度(相対密度)を上げるために、酸化雰囲気で焼結する必要があるが、その場合、ターゲットの抵抗を下げるため、焼結後に高温での還元処理が必要となる問題があった。また、ターゲットを長期間使用していると得られた膜の特性や成膜速度が大きく変化する、InGaZnO4やIn2Ga2ZnO7の異常成長による異常放電が起きる、成膜時にパーティクルの発生が多い等の問題があった。
また、In、Ga及びZnの原子比がほぼ同量の場合の検討が中心であり、Znが少なくGaが多い組成(例えば、原子比In:Ga:Zn=40:40:20などZn30原子%未満、Ga35原子%以上の組成)での具体的な検討は十分ではなかった(特許文献2、3、4)。
このように、酸化物半導体膜をスパッタリングで作製する際に使用するターゲットについての検討は十分ではなかった。
尚、ZnGa2O4にIn2O3をドープした酸化物は蛍光体として検討されているが、In2O3で表されるビックスバイト構造を示す化合物の含有量が少なく、抵抗が高いものであった。従って、酸化物焼結体やスパッタリングターゲットとしては検討されていなかった(非特許文献3)。
本発明によれば、以下の酸化物焼結体等が提供される。
1.In(インジウム元素)、Ga(ガリウム元素)及びZn(亜鉛元素)を含み、
酸素元素を除く全元素に対する、In,Ga及びZnの合計含有率が95原子%以上であり、
In2O3で表されるビックスバイト構造を示す化合物と、ZnGa2O4で表されるスピネル構造を示す化合物とを含む、酸化物焼結体。
2.前記In、Ga及びZnの合計に対するGaの原子比が下記式(1)を満たし、
前記In、Ga及びZnの合計に対するZnの原子比が下記式(2)を満たす、1に記載の酸化物焼結体。
0.20<Ga/(In+Ga+Zn)<0.49 (1)
0.10<Zn/(In+Ga+Zn)<0.30 (2)
3.前記In2O3で表されるビックスバイト構造を示す化合物、及び前記ZnGa2O4で表されるスピネル構造を示す化合物のいずれか一方が第一成分(主成分)であり、他方が第二成分(副成分)である1又は2に記載の酸化物焼結体。
4.前記In2O3で表されるビックスバイト構造を示す化合物の、X線回折(XRD)における最大ピーク強度(I(In2O3))と、前記ZnGa2O4で表されるスピネル構造を示す化合物の最大ピーク強度(I(ZnGa2O4))の比(I(ZnGa2O4)/I(In2O3))が、0.80以上1.25以下である1~3のいずれかに記載の酸化物焼結体。
5.相対密度が90%以上、四探針法で測定した抵抗率が50mΩcm以下、及び表面の黒点の数が0.1個/cm2以下である1~4のいずれかに記載の酸化物焼結体。
6.含有される金属元素が、実質的にIn,Ga及びZnである1~5のいずれかに記載の酸化物焼結体。
7.
さらに、正四価元素Xを含有し、
In、Ga、Zn及びXの合計に対するXの原子比が下記式(3)を満たす、1~5のいずれかに記載の酸化物焼結体。
0.0001<X/(In+Ga+Zn+X)<0.05 (3)
8.前記Xが、Sn,Ge,Zr,Hf,Ti,Si,Mo及びWからなる群より選択される少なくとも1つである7に記載の酸化物焼結体。
9.含有される金属元素が、実質的にIn,Ga,Zn及び正四価元素Xである7又は8に記載の酸化物焼結体。
10.1~9のいずれかに記載の酸化物焼結体からなるスパッタリングターゲット。
11.酸化インジウム粉、酸化ガリウム粉及び酸化亜鉛粉を含む原料からなる成形体を、1160~1380℃で1~80時間焼結する工程を含む、1~9のいずれかに記載の酸化物焼結体の製造方法。
12.焼結工程の酸素加圧が1~3気圧である11に記載の酸化物焼結体の製造方法。
13.10に記載のスパッタリングターゲットを用いアモルファス酸化物膜を成膜する工程を含む、半導体素子の作製方法。
具体的には、ICP-AESを用いた分析では、溶液試料をネブライザーで霧状にして、アルゴンプラズマ(約6000~8000℃)に導入すると、試料中の元素は熱エネルギーを吸収して励起され、軌道電子が基底状態から高いエネルギー準位の軌道に移る。この軌道電子は10-7~10-8秒程度で、より低いエネルギー準位の軌道に移る。この際にエネルギーの差を光として放射し発光する。この光は元素固有の波長(スペクトル線)を示すため、スペクトル線の有無により元素の存在を確認できる(定性分析)。
また、それぞれのスペクトル線の大きさ(発光強度)は試料中の元素数に比例するため、既知濃度の標準液と比較することで試料濃度を求めることができる(定量分析)。
定性分析で含有されている元素を特定後、定性分析で含有量を求め、その結果から各元素の原子比を求める。
ここで、「In2O3で表されるビックスバイト構造」(希土類酸化物C型の結晶構造)とは、(Th 7,Ia3)の空間群を持つ立方晶系のことであり、Mn2O3(I)型酸化物結晶構造とも言う。例えば、Sc2O3、Y2O3、Tl2O3、Pu2O3、Am2O3、Cm2O3、In2O3、ITO(In2O3に10wt%程度以下のSnをドープしたもの)がこの結晶構造を示す(「透明導電膜の技術」参照)。酸化物焼結体が、In2O3で表されるビックスバイト構造を示す化合物を含むことは、X線回折(XRD)でJCPDSカードNo.6-0416のパターンを示すことから確認できる。
さらに、In2O3で表されるビックスバイト構造の結晶構造は酸素欠損を作りやすい。従って、還元処理を行わなくともIn2O3で表されるビックスバイト構造の結晶構造に酸素欠損が生成させ低抵抗化することが可能である。
酸化物結晶中に含まれる酸素イオンの数は、例えば、酸化物結晶を炭素粉末中で加熱させて生成する二酸化炭素の量を赤外吸収スペクトルで測定することで算出することができる。また、化学量論量の酸素イオンの数は酸化物結晶の質量から算出することができる。
0.20<Ga/(In+Ga+Zn)<0.49 (1)
0.10<Zn/(In+Ga+Zn)<0.30 (2)
一方、Gaの原子比が0.49未満であれば、酸化物焼結体の密度を高めやすく、また、抵抗を下げやすい。
Gaの原子比[Ga/(In+Ga+Zn)]は、0.25以上0.48以下であることが好ましく、さらに、0.35以上0.45以下であることが好ましく、特に、0.37以上0.43以下であることが好ましい。
一方、Znの原子比が0.30未満であれば、上述した結晶型を含む焼結体が得やすくなる。また、得られる薄膜を使用することで、TFT特性の均一性や再現性を向上させることができる。
Znの原子比[Zn/(In+Ga+Zn)]は、0.15以上0.25以下であることが好ましく、さらに、0.17以上0.23以下であることが好ましい。
一方、Inの原子比が0.55未満であると、酸化物焼結体の密度を高めやすく、また、抵抗を下げやすい。
Inの原子比[In/(In+Ga+Zn)]は、0.25以上0.50以下であることが好ましく、さらに、0.35以上0.45以下であることが好ましく、特に、0.37以上0.43以下であることが好ましい。
上記最大ピーク強度比は、0.90以上1.10以下であることがより好ましく、特に0.95以上1.05以下であることが好ましい。0.99以上1.05以下であるとさらに好ましい。
尚、X線回析における最大ピーク強度とは、最も高いピークのピーク高さを意味する(メインピークと呼ぶ場合もある)。ピークの帰属はJCPDSカードのパターンと比較して判断する。パターンが一致していればピークシフトしていてもよい。In2O3で表されるビックスバイト構造を示す化合物の最大ピーク強度(I(In2O3))は通常30~31°付近に、ZnGa2O4で表されるスピネル構造を示す化合物の最大ピーク強度は通常35~36°付近に確認される。
尚、ピーク位置のずれは、格子定数(a)の変化を示し、aは10.05以上10.10未満であることが好ましい。aが10.10未満だと原子間の距離が短くなり移動度が向上することが期待できる。ただし、aが10.05未満だと、構造のゆがみが大きくなり対象性が崩れ、散乱により移動度が低下するおそれがある。
最大ピークが重なる場合は、他のピークから最大ピークを算出することが可能である。具体的にはICDD(International Center for Diffraction Data)に掲載されている強度比データを用いて、最大ピーク以外のピーク強度を逆算することにより最大ピークを求めることができる。
ここで、Inリッチ相とは、周囲に比べてインジウム含有量が多い相を意味する。同様に、Gaリッチ相とは、周囲に比べてガリウム含有量が多い相を意味する。Inリッチ相またはGaリッチ相であることは、X線マイクロアナライザー(Electron Probe Micro Analysis)(EPMA)により確認できる。
各相の粒径は平均200μm以下が好ましく、平均100μm以下がより好ましく、平均50μ以下がさらに好ましく、特に平均20μm以下であることが、スパッタリングが安定するため好ましい。各相の粒径に下限はないが、通常0.1μm以上である。
Inリッチ相が周囲の相よりも酸素含有率が低いことが好ましい。Inリッチ相の酸素含有率が周囲の相よりも低いことは、EPMAで確認できる。
相対密度が90%以上であれば、酸化物焼結体の抵抗が低くなり、抗折強度も高くなる。相対密度は95%以上がより好ましく、98%以上がさらに好ましく、99%以上が特に好ましい。
尚、相対密度とは、加重平均より算出した理論密度に対して相対的に算出した密度である。各原料の密度の加重平均より算出した密度が理論密度であり、これを100%とする。
尚、抵抗率は抵抗率計を使用し、四探針法により測定した値である。
尚、表面の黒点の数は、北窓昼光下で目視にて数えた黒点の数を観察した総面積で除して求める。
0.0001<X/(In+Ga+Zn+X)<0.05 (3)
Xの原子比が0.0001超であれば、正四価元素Xの添加効果が発現し、酸化物焼結体の相対密度の向上や抵抗の低下が期待できる。好ましくは、0.0003以上であり、特に好ましくは0.0005以上である。
一方、Xの原子比が0.05未満であると、In2O3で表されるビックスバイト構造を示す化合物とZnGa2O4で表されるスピネル構造が得られ易く本発明の特性が得られやすい。好ましくは、0.04以下であり、特に好ましくは0.03以下である。
Xを添加することにより、薄膜トランジスタとした際に正四価元素の低級酸化物が生成し、トランジスタ特性が低下するおそれが少なくなる。また、ターゲットの厚み方向で構造が変化することによる特性のムラが発生することが少ない。
尚、Xの原子比が0.05以上の場合、Xの低級酸化物の生成が過剰となり、酸化物焼結体の抵抗が高くなるおそれがある。また、トランジスタを作製した際に移動度が低下する等のおそれがある。
酸化物焼結体の密度向上や比抵抗の抑制の観点からは、Sn、Ge、Si、Ti、Zr、Hf、V、Nb、Ta、Mo、W、Mn、Ceが好ましく、Sn、Ge、Si、Ti、Zr、Hfがさらに好ましく、Sn、Ge、Si、Zrがより好ましく、Snが特に好ましい。
また、酸化物焼結体を使用して成膜した薄膜を有する薄膜トランジスタの均一性や再現性を向上させるには、Sn、Ge、Si、Zrが好ましく、Sn、Zrがさらに好ましく、Snが特に好ましい。
本発明では、Xは、Sn,Ge,Zr,Hf,Ti,Si,Mo及びWからなる群より選択される少なくとも1つであることが好ましい。
酸化物焼結体中において、直径10μm以上の酸化スズの凝集粒子数は、1.00mm2あたり2.5個以下であることが好ましい。これにより、酸化スズの凝集粒子による異常放電を低減できる。
しかしながら、本発明においては、酸化物焼結体に含有される金属元素は、実質的にIn,Ga及びZnのみ、又はIn,Ga,Zn及びXのみであってもよい。尚、「実質的」とは、原料や製造工程等により不可避的に含まれる不純物等以外の元素を含まないことを意味する。
尚、原料としてIn-Zn酸化物、In-Ga酸化物、Ga-Zn酸化物等の複合酸化物を使用してもよい。特にIn-Zn酸化物、又はGa-Zn酸化物を用いると、Znの昇華を抑制することができるため好ましい。また、In2O3粉末とZnGa2O3粉末を原料として用いると、本発明の焼結体が得られやすく、かつZnの昇華も抑制できるので、より好ましい。
ここで、各粉体の比表面積はBET法で測定した値である。各粉体の粒度分布のメジアン径は、粒度分布計で測定した値である。これらの値は、粉体を乾式粉砕法、湿式粉砕法等により粉砕することにより調整できる。
焼結時間を1時間以上とすることにより、焼結不足によるばらつきが防止できる。また、100時間以下とすることにより焼結後の反りや変形を防止できる。
このようにして製造した焼結体は、密度が高いため、使用時におけるノジュールやパーティクルの発生が少ないことから、膜特性に優れた酸化物半導体膜を作製することができる。
鏡面加工(研磨)は機械的な研磨、化学研磨、メカノケミカル研磨(機械的な研磨と化学研磨の併用)等の、すでに知られている研磨技術を用いることができる。例えば、固定砥粒ポリッシャー(ポリッシュ液:水)で#2000以上にポリッシングしたり、又は遊離砥粒ラップ(研磨材:SiCペースト等)にてラッピング後、研磨材をダイヤモンドペーストに換えてラッピングすることによって得ることができる。このような研磨方法には特に制限はない。
エアーブローや流水洗浄の他に、超音波洗浄等を行なうこともできる。超音波洗浄では、周波数25~300KHzの間で多重発振させて行なう方法が有効である。例えば周波数25~300KHzの間で、25KHz刻みに12種類の周波数を多重発振させて超音波洗浄を行なうのがよい。
還元性ガスによる還元処理の場合、水素、メタン、一酸化炭素や、これらのガスと酸素との混合ガス等を用いることができる。不活性ガス中での焼成による還元処理の場合、窒素、アルゴンや、これらのガスと酸素との混合ガス等を用いることができる。尚、還元処理時の温度は、通常100~800℃、好ましくは200~800℃である。また、還元処理の時間は、通常0.01~10時間、好ましくは0.05~5時間である。
粒径は、例えば、原料である各酸化物の粉体の配合比や原料粉体の粒径、純度、昇温時間、焼結温度、焼結時間、焼結雰囲気、降温時間を調製することにより制御できる。化合物の粒径が20μmより大きいとスパッタ時にノジュールが発生するおそれがある。また、200μmより大きいとターゲット表面に凹凸が発生し、成膜時の異常放電の原因となりやすい。
ターゲットの表面粗さRaは0.5μm以下であり、方向性のない研削面を備えていることが好ましい。Raが0.5μmより大きかったり、研磨面に方向性があると、異常放電が起きたり、パーティクルが発生するおそれがある。
ターゲット内におけるフェレー径2μm以上のピンホール数が単位面積当たり50個/mm2以下が好ましく、20個/mm2以下がより好ましく、5個/mm2以下がさらに好ましい。焼結体内部のフェレー径2μm以上のピンホール数が50個/mm2より多いと、ターゲット使用初期から末期までに異常放電が多発するようになる。また、得られるスパッタ膜の平滑性も低下する傾向にある。焼結体内部のフェレー径2μm以上のピンホールが5個/mm2以下だと、ターゲット使用初期から末期まで異常放電を抑制でき、また、得られるスパッタ膜は非常に平滑である。
ここで、フェレー径とは、ピンホールを粒子として見立てた場合に、粒子を挟むある一定方向の平行線間隔のことをいう。例えば、倍率100倍のSEM像による観察で計測できる。
一方、酸化物焼結体の窒素含有量が5ppm超の場合、得られるターゲットのスパッタリング時の異常放電、及びターゲット表面への吸着ガス量を十分に抑制できないおそれがあるうえ、ターゲット中の窒素とインジウムがスパッタリング時に反応して黒色窒化インジウム(InN)を生成して、半導体膜中に混入して歩留まりが低下するおそれがある。これは、窒素原子が5ppm超含まれる場合、窒素原子が可動イオンとなりゲート電圧ストレスにより半導体界面に集まりトラップを生成するため、あるいは窒素がドナーとして働き性能を低下させるためと推測される。
窒素含有量を5ppm(原子)以下とするには、焼結を非窒素雰囲気(例えば酸素雰囲気)で行い、かつ窒素含有雰囲気下での還元処理を行わないことが好ましい。また、酸素流入下で焼結すると残留窒素が放出されるためより好ましい。
TNでは、含窒素無機物又は含窒素有機物を触媒存在下で分解させ、Nを一酸化窒素(NO)に変換し、このNOガスをオゾンと気相反応させ、化学発光により光を発し、その発光強度からNの定量を行う。
本発明のターゲットを使用して成膜することによりアモルファス酸化物膜が得られる。この膜は、薄膜トランジスタ等の半導体素子の構成部材として好適に使用できる。
以下、本発明により得られる酸化物膜を薄膜トランジスタに適用した例を説明する。
薄膜トランジスタ1は、基板10及びゲート絶縁膜30の間にゲート電極20を挟持しており、ゲート絶縁膜30上には半導体膜40が活性層(チャンネル層)として積層されている。半導体膜40の上部にはエッチストッパー60が形成されている。半導体膜40の端部付近及びエッチストッパー60の端部付近を覆うようにしてソース電極50及びドレイン電極52がそれぞれ設けられている。
以下、薄膜トランジスタの部材について説明する。
特に制限はなく、本技術分野で公知のものを使用できる。例えば、ケイ酸アルカリ系ガラス、無アルカリガラス、石英ガラス等のガラス基板、シリコン基板、アクリル、ポリカーボネート、ポリエチレンナフタレート(PEN)等の樹脂基板、ポリエチレンテレフタレート(PET)、ポリアミド等の高分子フィルム基材等が使用できる。
上述したように、本発明の酸化物焼結体からなるスパッタリングターゲットにより得られる膜を使用する。半導体層は非晶質膜であることが好ましい。非晶質膜であることにより、絶縁膜や保護層との密着性が改善できる、大面積でも均一なトランジスタ特性が容易に得られることとなる。ここで、半導体層が非晶質膜であるかは、X線結晶構造解析により確認できる。明確なピークが観測されない場合が非晶質である。
保護層を形成する材料は特に制限はない。本発明の効果を失わない範囲で一般に用いられているものを任意に選択できる。例えば、SiO2,SiNx,Al2O3,Ta2O5,TiO2,MgO,ZrO2,CeO2,K2O,Li2O,Na2O,Rb2O,Sc2O3,Y2O3,Hf2O3,CaHfO3,PbTi3,BaTa2O6,SrTiO3,AlN等を用いることができる。これらのなかでも、SiO2,SiNx,Al2O3,Y2O3,Hf2O3,CaHfO3を用いるのが好ましく、より好ましくはSiO2,SiNx,Y2O3,Hf2O3,CaHfO3であり、特に好ましくはSiO2,Y2O3,Hf2O3,CaHfO3等の酸化物である。これらの酸化物の酸素数は、必ずしも化学量論比と一致していなくともよい(例えば、SiO2でもSiOxでもよい)。また、SiNxは水素元素を含んでいても良い。
保護膜は、異なる2層以上の絶縁膜を積層した構造でもよい。
ゲート絶縁膜を形成する材料にも特に制限はなく、一般に用いられているものを任意に選択できる。例えば、SiO2,SiNx,Al2O3,Ta2O5,TiO2,MgO,ZrO2,CeO2,K2O,Li2O,Na2O,Rb2O,Sc2O3,Y2O3,Hf2O3,CaHfO3,PbTi3,BaTa2O6,SrTiO3,AlN等を用いることができる。これらのなかでも、SiO2,SiNx,Al2O3,Y2O3,Hf2O3,CaHfO3を用いるのが好ましく、より好ましくはSiO2,SiNx,Y2O3,Hf2O3,CaHfO3である。これらの酸化物の酸素数は、必ずしも化学量論比と一致していなくともよい(例えば、SiO2でもSiOxでもよい)。また、SiNxは水素元素を含んでいても良い。
ゲート絶縁膜は、異なる2層以上の絶縁膜を積層した構造でもよい。また、ゲート絶縁膜は、結晶質、多結晶質、非晶質のいずれであってもよいが、工業的に製造しやすい多結晶質か、非晶質であるのが好ましい。
また、ゲート絶縁膜は、ポリ(4-ビニルフェノール)(PVP)、パリレン等の有機絶縁膜を用いてもよい。さらに、ゲート絶縁膜は無機絶縁膜及び有機絶縁膜の2層以上積層構造を有してもよい。
ゲート電極、ソ-ス電極及びドレイン電極の各電極を形成する材料に特に制限はなく、一般に用いられているものを任意に選択することができる。
例えば、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物、ZnO、SnO2等の透明電極や、Al,Ag,Cr,Ni,Mo,Au,Ti,Ta、Cu等の金属電極、又はこれらを含む合金の金属電極を用いることができる。
具体的に、成膜方法としては、スプレー法、ディップ法、CVD法等の化学的成膜方法、又はスパッタ法、真空蒸着法、イオンプレーティング法、パルスレーザーディポジション法等の物理的成膜方法を用いることができる。キャリア密度が制御し易い、及び膜質向上が容易であることから、好ましくは物理的成膜方法を用い、より好ましくは生産性が高いことからスパッタ法を用いる。
本発明では半導体層を、本発明の酸化物焼結体からなるターゲットを用い、DC又はACスパッタリングにより成膜する。DC又はACスパッタリングを用いることにより、RFスパッタリングの場合と比べて、成膜時のダメージを低減できる。このため、電界効果型トランジスタにおいて、移動度の向上等の効果が期待できる。
また、本発明では半導体層と半導体の保護層を形成した後に、70~350℃で熱処理することが好ましい。70℃より低いと得られるトランジスタの熱安定性や耐熱性が低下したり、移動度が低くなったり、S値が大きくなったり、閾値電圧が高くなるおそれがある。一方、350℃より高いと耐熱性のない基板が使用できなかったり、熱処理用の設備費用がかかるおそれがある。
熱処理は、不活性ガス中で酸素分圧が10-3Pa以下の環境下で行うか、あるいは半導体層を保護層で覆った後に行うことが好ましい。上記条件下だと再現性が向上する。
オンオフ比は、106以上が好ましく、107以上がより好ましく、108以上が特に好ましい。
原料粉として、In2O3(比表面積:11m2/g、純度99.99%)、Ga2O3(比表面積:11m2/g、純度99.99%)及びZnO(比表面積:9m2/g、純度99.99%)の各粉末を使用した。表1に示す原子組成比となるように原料を混合し、スーパーミキサーで4分間混合した。混合は大気中にて、回転数3000rpmにて行った。
得られた混合粉を電気炉にて、大気雰囲気中1000℃で5時間程度保持し、仮焼した。得られた仮焼粉をジルコニアビーズと共にアトライターに投入し、回転数300rpmで3時間微粉砕した。微粉砕した結果、原料粉の粒径は平均粒径(D50)で0.55μmとなった。
微粉砕した原料粉に、固形分が50重量%のスラリー(泥漿)となるように水を加えた。このスラリーを造粒装置にて造粒した。尚、装置の入り口温度を200℃、出口温度を120℃に設定した。
次に、電気炉にて酸素雰囲気(酸素加圧2気圧)中、昇温速度0.5℃/minmで800℃まで昇温し、800℃で5時間保持した。その後、昇温速度1.0℃/minで1300℃まで昇温し、1300℃で20時間保持した。
その後、炉冷で降温し焼結体を得た(降温速度は0.5℃/min以上であった)。
尚、本実施例では無酸素下の熱処理等による還元処理は行わなかった。
得られた焼結体を粉砕しICP発光分析装置(島津製作所社製)で分析したところ、含有金属元素の原子比(In:Ga:Zn)は40:40:20であった。
(1)相対密度
原料粉の密度から計算した理論密度とアルキメデス法で測定した焼結体の密度から下記式で計算して求めた。
相対密度(%)=(アルキメデス法で測定した密度)÷(理論密度)×100
(2)抵抗率
抵抗率計(三菱化学(株)製、ロレスタ)を使用し四探針法(JIS R 1637)に基づき測定し、10箇所の平均値を抵抗率とした。
(3)表面の黒点密度
10個のターゲットを作製し、北窓昼光下、目視で数えた黒点の数を観察した総面積で除して求めた。
(4)坑折強度(曲げ強さ)
抗折試験器(オートグラフ、島津製作所社製)を用いてJIS R1601に基づいて評価した。
(5)焼結時のクラック(ひび割れ)
5個のターゲット(焼結体)を焼結直後に肉眼で目視し、クラック発生の有無を確認した。
(6)X線回折測定(XRD)
・装置:(株)リガク製Ultima-III
・X線:Cu-Kα線(波長1.5406Å、グラファイトモノクロメータにて単色化)
・2θ-θ反射法、連続スキャン(1.0°/分)
・サンプリング間隔:0.02°
・スリット DS、SS:2/3°、RS:0.6mm
図2-5に、実施例1,2及び比較例1,2で作製した焼結体の表面のX線回折(XRD)データを示す。
尚、In2O3で表されるビックスバイト構造を示す化合物の、X線回折(XRD)における最大ピーク強度(I(In2O3))と、ZnGa2O4で表されるスピネル構造を示す化合物の最大ピーク強度(I(ZnGa2O4))の比(I(ZnGa2O4)/I(In2O3))は、実施例1で1.04、実施例2で1.03であった。尚、In2Ga2ZnO7やInGaZnO4で表されるホモロガス結晶構造を示す化合物は確認できなかった。
また、EPMAの測定により、Inリッチ相及びGaリッチ相を有することが確認できた。また、Inリッチ層が他の層よりも酸素含有率が低いことが確認できた。
さらに、微量全窒素分析装置(TN)で測定した焼結体中の窒素含有量は5ppm以下であった。
表1に示すように、組成及び焼結条件を変えた他は、実施例1と同様にしてターゲット及びTFTを作製し評価した。結果を表1に示す。
(A)酸化物焼結体の作製
比表面積15m2/g、純度99.99%のIn2O3粉、比表面積14m2/g、純度99.99%のGa2O3粉、及び比表面積4m2/g、純度99.99%のZnO粉末を配合し、ボールミルにて各原料粉末の粒度が1μm以下になるまで混合、粉砕を行った。作製したスラリーを取り出して、スラリー供給速度140ml/min、熱風温度140℃、熱風量8Nm3/minの条件で、スプレードライヤを用いて急速乾燥造粒した。造粒物を冷間静水圧プレスにて3ton/cm2の圧力で成形し、成形体を得た。
次に、この成形体を焼結した。焼結における昇温は、600℃までは大気中にて0.5℃/minの速度で昇温し、その後、600~800℃までは酸素ガスを10L/minの流速で導入しながら1℃/minの速度で昇温した。さらに、800~1300℃の温度範囲では3℃/minの速度で昇温した。酸素加圧は2気圧であった。その後、1300℃にて20時間の保持し、1℃/minで降温して焼結体を得た。尚、無酸素下の熱処理等による還元処理は行わなかった。
焼結体の性状及び物性を実施例1と同様に評価した。結果を表2-5に示す。
上記で作製した焼結体からターゲット用焼結体を切り出し、ターゲット用焼結体の側辺をダイヤモンドカッターで切断して、表面を平面研削盤で研削して表面粗さRa5μm以下のターゲット素材とした。
次に、表面をエアーブローし、さらに周波数25~300kHzの間で25kHz刻みに12種類の周波数を多重発振させて3分間超音波洗浄を行なった。この後、ターゲット素材をインジウム半田にて無酸素銅製のバッキングプレートにボンディングしてターゲットとした。
相対密度のばらつき(%)=(最大-最小)/平均×100
また、平均空孔数は焼結体の任意の方向にて鏡面研磨後、エッチングし、組織をSEM(走査型電子顕微鏡)で観察し、単位面積当たりの直径1μm以上の空孔の個数を数えた。
・RFスパッタリング
(1)異常放電
3時間あたりに発生する異常放電回数を測定した。評価は、5回以下をA、6回以上10回以下をB、11回以上20回以下をC、21回以上30回以下をDとした。
(2)面内均一性
同一面内の比抵抗の最大値と最小値の比(最大値/最小値)を測定した。その結果、比抵抗の均一性の良い方から順に、1.05以内をA、1.05より大であり1.10以内をB、1.10より大であり1.20以内をC、1.20より大をDとして、4段階で評価した。
・DCスパッタリング
(1)異常放電
96時間で発生した異常放電回数を測定した。
(2)ノジュールの発生
以下のとおり評価した。
A:ほとんど無、B:若干あり、C:有り、D:多発、E:成膜不可
(3)連続安定性
成膜性について、連続20バッチ分における第1バッチと第20バッチの平均電界効果移動度の比(第1バッチ/第20バッチ)を測定した。その結果、TFT特性の再現性の良い方から順に、1.10以内をA、1.10より大であり1.20以内をB、1.20より大であり1.50以内をC、1.50より大をDとして、4段階で評価した。
(4)面内均一性
同一面内の比抵抗の最大値と最小値の比(最大値/最小値)を測定した。その結果、比抵抗の均一性の良い方から順に、1.05以内をA、1.05より大であり1.10以内をB、1.10より大であり1.20以内をC、1.20より大をDとして、4段階で評価した。
(5)ターゲットのクラック発生
10個のスパッタリングターゲットに発生するクラッキング(ターゲットのクラック発生)を成膜直後に肉眼で目視し、クラックの有無を確認した。その結果、10個のターゲットに全くクラックが発生しなかったものをA、1個のターゲットにクラックが発生したものをB、2個以上のターゲットにクラックが発生したものをDとして、評価した。
図1に示すチャンネルストッパー型薄膜トランジスタ(逆スタガ型薄膜トランジスタ)を作製した。
基板10は、ガラス基板(Corning 1737)を用いた。まず、基板10上に電子ビーム蒸着法により、厚さ10nmのMoと厚さ80nmのAlと厚さ10nmのMoをこの順で積層した。積層膜をフォトリソグラフィー法とリフトオフ法を用いて、ゲート電極20に形成した。
ゲート電極20及び基板10上に、厚さ200nmのSiO2膜をTEOS-CVD法により成膜し、ゲート絶縁層30を形成した。尚、ゲート絶縁層の成膜はスパッタ法でもよいが、TEOS-CVD法やPECVD法等のCVD法で形成することが好ましい。スパッタ法ではオフ電流が高くなるおそれがある。
続いて、RFスパッタ法により、上記(B)で作製したターゲットを使用して、厚さ40nmの半導体膜40(チャネル層)を形成した。半導体膜40の上に、スパッタ法によりエッチングストッパー層60(保護膜)としてSiO2膜を堆積した。尚、保護膜の成膜方法はCVD法でもよい。
本実施例では、投入RFパワーは200Wとしている。成膜時の雰囲気は、全圧0.4Paであり、その際のガス流量比はAr:O2=92:8である。また、基板温度は70℃である。堆積させた酸化物半導体膜と保護膜は、フォトリソグラフィー法及びエッチング法により、適当な大きさに加工した。
エッチングストッパー層60の形成後に、厚さ5nmのMoと厚さ50nmのAlと厚さ5nmのMoをこの順で積層し、フォトリソグラフィー法とドライエッチングにより、ソース電極50及びドレイン電極52を形成した。
その後、大気中300℃で60分間熱処理し、チャネル長が10μmで、チャネル幅が100μmのトランジスタを作製した。尚、基板(TFTパネル)内には10行×10列で、合計100個のTFTを等間隔で配列して形成した。
ターゲット及び薄膜トランジスタの評価結果を表2-5に示す。尚、薄膜トランジスタの評価は、以下のように実施した。
半導体パラメーターアナライザー(ケースレー4200)を用い、室温、遮光環境下で測定した。
(2)TFT特性の均一性
同一パネル内のVg=6Vにおけるオン電流の最大値と最小値の比(最大値/最小値)を測定した。最大値と最小値の比を以下の基準で分類し、評価した。
1.05以内:A、 1.10以内:B、 1.20以内:C、 1.20超:D
連続5バッチ分における第1バッチと第5バッチの平均電界効果移動度の比(第1バッチ/第5バッチ)を測定した。平均電界効果移動度の比を以下の基準で分類し、評価した。
1.10以内:A、 1.20以内:B、 1.50以内:C、 1.50超:D
連続10バッチ分のパネルについて、各同一パネル内の100個のTFT(合計1000個)の駆動確認を行い、駆動したTFTの数を数えた。但し、短絡して駆動しなかったTFTは除いた。駆動したTFTの数を以下の基準で分類し、評価した
999個以上駆動:A、 995個以上999個未満駆動:B、 990個以上995個未満駆動:C、 990個未満駆動:D
表2、3に示すように、原料、組成及び製造条件等を変えた他は、実施例3と同様にして、ターゲット及び薄膜トランジスタを作製し、評価した。結果を表2-5に示す。
尚、酸化錫としては、株式会社高純度化学研究所製のSNO06PBを用いた。Geの酸化物としては、株式会社高純度化学研究所製のGEO07PBを用いた。
Hfの酸化物としては、株式会社高純度化学研究所製のHFO01PBを用いた。
Tiの酸化物としては、株式会社高純度化学研究所製のTIO14PBを用いた。
Siの酸化物としては、株式会社高純度化学研究所製のSIO14PBを用いた。
Moの酸化物としては、株式会社高純度化学研究所製のMOO01PBを用いた。Wの酸化物としては、株式会社高純度化学研究所製のWWO04PBを用いた。
Zrの酸化物としては、株式会社高純度化学研究所製のZRO02PBを用いた。
酸化錫:6m2/g
Ge、Zr、Hf,Ti,Siの各酸化物:10m2/g
Mo、Wの各酸化物:8m2/g
実施例3において、大気下、1400℃2時間で焼結を行った他は、実施例3と同様にして、ターゲット及び薄膜トランジスタを作製し、評価した。結果を表6,7に示す。
この明細書に記載の文献の内容を全てここに援用する。
Claims (13)
- In(インジウム元素)、Ga(ガリウム元素)及びZn(亜鉛元素)を含み、
酸素元素を除く全元素に対する、In,Ga及びZnの合計含有率が95原子%以上であり、
In2O3で表されるビックスバイト構造を示す化合物と、ZnGa2O4で表されるスピネル構造を示す化合物とを含む、酸化物焼結体。 - 前記In、Ga及びZnの合計に対するGaの原子比が下記式(1)を満たし、
前記In、Ga及びZnの合計に対するZnの原子比が下記式(2)を満たす、請求項1に記載の酸化物焼結体。
0.20<Ga/(In+Ga+Zn)<0.49(1)
0.10<Zn/(In+Ga+Zn)<0.30(2) - 前記In2O3で表されるビックスバイト構造を示す化合物、及び前記ZnGa2O4で表されるスピネル構造を示す化合物のいずれか一方が第一成分(主成分)であり、他方が第二成分(副成分)である請求項1又は2に記載の酸化物焼結体。
- 前記In2O3で表されるビックスバイト構造を示す化合物の、X線回折(XRD)における最大ピーク強度(I(In2O3))と、前記ZnGa2O4で表されるスピネル構造を示す化合物の最大ピーク強度(I(ZnGa2O4))の比(I(ZnGa2O4)/I(In2O3))が、0.80以上1.25以下である請求項1~3のいずれかに記載の酸化物焼結体。
- 相対密度が90%以上、四探針法で測定した抵抗率が50mΩcm以下、及び表面の黒点の数が0.1個/cm2以下である請求項1~4のいずれかに記載の酸化物焼結体。
- 含有される金属元素が、実質的にIn,Ga及びZnである請求項1~5のいずれかに記載の酸化物焼結体。
- さらに、正四価元素Xを含有し、
In、Ga、Zn及びXの合計に対するXの原子比が下記式(3)を満たす、請求項1~5のいずれかに記載の酸化物焼結体。
0.0001<X/(In+Ga+Zn+X)<0.05(3) - 前記Xが、Sn,Ge,Zr,Hf,Ti,Si,Mo及びWからなる群より選択される少なくとも1つである請求項7に記載の酸化物焼結体。
- 含有される金属元素が、実質的にIn,Ga,Zn及び正四価元素Xである請求項7又は8に記載の酸化物焼結体。
- 請求項1~9のいずれかに記載の酸化物焼結体からなるスパッタリングターゲット。
- 酸化インジウム粉、酸化ガリウム粉及び酸化亜鉛粉を含む原料からなる成形体を、1160~1380℃で1~80時間焼結する工程を含む、請求項1~9のいずれかに記載の酸化物焼結体の製造方法。
- 焼結工程の酸素加圧が1~3気圧である請求項11に記載の酸化物焼結体の製造方法。
- 請求項10に記載のスパッタリングターゲットを用いアモルファス酸化物膜を成膜する工程を含む、半導体素子の作製方法。
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201119971A (en) | 2011-06-16 |
| JPWO2011040028A1 (ja) | 2013-02-21 |
| CN102482156A (zh) | 2012-05-30 |
| KR20120091026A (ko) | 2012-08-17 |
| US20120184066A1 (en) | 2012-07-19 |
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