US20060108624A1 - Semiconductor device - Google Patents
Semiconductor device Download PDFInfo
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- US20060108624A1 US20060108624A1 US11/024,422 US2442204A US2006108624A1 US 20060108624 A1 US20060108624 A1 US 20060108624A1 US 2442204 A US2442204 A US 2442204A US 2006108624 A1 US2006108624 A1 US 2006108624A1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 claims abstract description 46
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 43
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000009792 diffusion process Methods 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 230000002265 prevention Effects 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 61
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 229910052697 platinum Inorganic materials 0.000 claims description 29
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 27
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 24
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910002353 SrRuO3 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910003031 (La,Sr)CoO3 Inorganic materials 0.000 claims description 2
- 229910002340 LaNiO3 Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 37
- 238000004544 sputter deposition Methods 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910052814 silicon oxide Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 11
- 239000010937 tungsten Substances 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 229910020289 Pb(ZrxTi1-x)O3 Inorganic materials 0.000 description 9
- 229910020273 Pb(ZrxTi1−x)O3 Inorganic materials 0.000 description 9
- 230000002349 favourable effect Effects 0.000 description 8
- 230000015654 memory Effects 0.000 description 8
- 238000004151 rapid thermal annealing Methods 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
- H10B53/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors characterised by the memory core region
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
- G11C11/21—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements
- G11C11/22—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements using ferroelectric elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D1/00—Resistors, capacitors or inductors
- H10D1/60—Capacitors
- H10D1/68—Capacitors having no potential barriers
- H10D1/682—Capacitors having no potential barriers having dielectrics comprising perovskite structures
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D1/00—Resistors, capacitors or inductors
- H10D1/60—Capacitors
- H10D1/68—Capacitors having no potential barriers
- H10D1/692—Electrodes
- H10D1/694—Electrodes comprising noble metals or noble metal oxides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D1/00—Resistors, capacitors or inductors
- H10D1/60—Capacitors
- H10D1/68—Capacitors having no potential barriers
- H10D1/692—Electrodes
- H10D1/696—Electrodes comprising multiple layers, e.g. comprising a barrier layer and a metal layer
Definitions
- the present invention relates to a semiconductor device having a capacitor.
- a typical ferroelectric film used for a ferroelectric memory is a Pb(Zr x Ti 1-x )O 3 film (PZT film) having a perovskite structure.
- electrodes are composed of conductive perovskite type metal oxide films such as SrRuO 3 films (SRO films) or the like in order to, for example, improve their fatigue characteristic.
- SRO films SrRuO 3 films
- Jpn. Pat. Appln. KOKAI Publication No. 2000-208725 and Jpn. Pat. Appln. KOKAI Publication No. 2000-260954 describe ferroelectric capacitors having electrodes each made of a stacked film composed of an SRO film and a Pt film.
- a COP Capacitor On Plug
- a bottom electrode of the capacitor is partly composed of an Ir film or Ir oxide film, which has an excellent oxygen barrier characteristic.
- Ir disadvantageously diffuses through the conductive perovskite type metal oxide film or a capacitor dielectric film, which degrades the characteristics or reliability of the capacitor.
- Ir may react with Pb in the PZT film to form a conductive oxide, which increases a leak current of the capacitor or Ir may react with Sr in the SRO film to degrade the crystallinity of the SRO film, which degrades the characteristics or reliability of a dielectric film on the SRO film.
- a problem with a capacitor having a capacitor dielectric film made of a metal oxide film having a perovskite structure is that the diffusion of Ir may degrade the characteristics or reliability of the capacitor.
- a semiconductor device comprising a capacitor provided above the semiconductor substrate and including a bottom electrode, a top electrode, and a dielectric film provided between the bottom electrode and the top electrode, the bottom electrode comprising a first conductive film containing iridium, a second conductive film provided between the dielectric film and the first conductive film and formed of a noble metal film, a third conductive film provided between the dielectric film and the second conductive film and formed of a conductive metal oxide film having a perovskite structure, and a diffusion prevention film provided between the first conductive film and the second conductive film and including at least one of a metal film and a metal oxide film, the diffusion prevention film preventing diffusion of iridium contained in the first conductive film, and the dielectric film including an insulating metal oxide film having a perovskite structure, the insulating metal oxide film being expressed by A(Zr x Ti 1-x )O 3 (A is at least one A site element, 0 ⁇ x ⁇ 0.3
- FIGS. 1 to 3 are sectional views schematically showing a method of manufacturing a semiconductor device according to a first embodiment of the present invention
- FIG. 4 is a graph showing a hysteresis characteristic of a capacitor according to the first embodiment of the present invention.
- FIG. 5 is a graph showing a hysteresis characteristic of a capacitor according to a comparative example of the first embodiment of the present invention.
- FIG. 6 is a graph showing the relationship between an x value and the quantity of switching charges for a Pb(Zr x Ti 1-x )O 3 film (PZT film) according to the first embodiment of the present invention
- FIG. 7 is a graph showing the intensity of an XRD pattern according to the first embodiment of the present invention.
- FIG. 8 is a graph showing the intensity of the XRD pattern according to a comparative example of the first embodiment of the present invention.
- FIG. 9 is a sectional view schematically showing a method of manufacturing a semiconductor device according to a second embodiment of the present invention.
- FIGS. 1 to 3 are sectional views schematically showing a method of manufacturing a semiconductor device according to a first embodiment of the present invention.
- an isolation region 101 of an STI (Shallow Trench Isolation) structure is formed on a p-type silicon substrate (semiconductor substrate) 100 .
- an MIS transistor is formed as described below.
- a silicon oxide film of thickness about 6 nm is formed by thermal oxidization.
- arsenic-doped n + type polysilicon film 103 is formed on the gate insulating film 102 .
- a WSi x film 104 and a silicon nitride film 105 are formed on the polysilicon film 103 .
- the polysilicon film 103 , the WSi x film 104 , and the silicon nitride film 105 are processed by a normal photo lithography process and a normal RIE process to form a gate electrode.
- a silicon nitride film 106 is deposited all over the surface of the resulting structure. Moreover, RIE is carried out to form side wall spacers formed of the silicon nitride film 106 , on side walls of the gate electrode.
- source/drain regions 107 are formed by ion implantation and thermal treatment.
- a CVD (Chemical Vapor Deposition) process is used to deposit a silicon oxide film 108 all over the surface of the resulting structure. Further, a CMP process is used to execute a flattening process. Subsequently, a contact hole is formed through the silicon oxide film 108 so as to reach one of the source/drain regions 107 . Then, a sputtering process or the CVD process is used to deposit a titanium film. Subsequently, the titanium film is nitrided by thermal treatment in a foaming gas to form a TiN film 110 . Moreover, the CVD process is used to deposit a tungsten film 111 .
- the CMP process is used to remove the TiN film 110 and tungsten film 111 from outside the contact hole, while leaving the TiN film 110 and the tungsten film 111 in the contact hole. This forms a plug connected to one of the source/drain regions 107 .
- the CVD process is used to deposit a silicon nitride film 112 all over the surface of the resulting structure. Furthermore, a control hole is formed so as to reach the other source/drain region 107 .
- a method similar to that described above is used to form a TiN film 114 and a tungsten film 115 in the contact hole. This forms a plug connected to the other source/drain region 107 .
- a titanium (Ti) film 116 of thickness about 10 nm is deposited by the sputtering process.
- a first conductive film 117 an iridium (Ir) film 117 a of about 100 nm thickness and an iridium oxide (IrO 2 ) film 117 b of about 50 nm thickness are sequentially deposited by the sputtering process.
- the iridium film 117 a and the iridium oxide film 117 b have an excellent oxygen barrier characteristic and can thus prevent the oxidization of the plug 115 during the subsequent thermal treatment step.
- a titanium (Ti) film 118 a of thickness about 2.5 nm is deposited by the sputtering process.
- the titanium film 118 a prevents the upward diffusion of the iridium contained in the iridium film 117 a and iridium oxide film 117 b.
- a platinum (Pt) film 119 of thickness about 50 nm is deposited by the sputtering process.
- a titanium film 120 of about 1.5 nm thickness is deposited by the sputtering process.
- an SrRuO 3 film (SRO film) 121 of thickness about 2.5 nm is deposited on the titanium film 120 by the sputtering process. Subsequently, the SRO film 121 is crystallized by RTA (Rapid Thermal Annealing) in an oxygen atmosphere.
- the SRO film 121 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C.
- a Pb(Zr x Ti 1-x )O 3 film (PZT film) 122 having a thickness of about 130 nm is formed by the sputtering process. Moreover, the PZT film 122 is crystallized by RTA in an oxygen atmosphere. In the present embodiment, the value of x is 0.30. That is, as the PZT film 122 , a Pb(Zr 0.3 Ti 0.7 )O 3 film is formed.
- an SRO film 123 having a thickness of about 10 nm is deposited by the sputtering process. Moreover, the SRO film 123 is crystallized by RTA in an oxygen atmosphere. The SRO film 123 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. Furthermore, a platinum film 124 of thickness about 50 nm is deposited by the sputtering process.
- the CVD process is used to deposit a silicon oxide film (not shown) all over the surface of the resulting structure.
- the photo lithography process and the RIE process are used to pattern the silicon oxide film.
- the patterned silicon oxide film is used as a mask to etch the platinum film 124 , the SRO film 123 , and the PZT film 122 by the RIE process.
- the photo lithography process and the RIE process are used to pattern the SRO film 121 , the titanium film 120 , the platinum film 119 , the titanium film 118 a, the iridium oxide film 117 b, the iridium film 117 a, and the titanium film 116 .
- a ferroelectric capacitor which comprises a bottom electrode having the titanium film 116 , the iridium film 117 a, the iridium oxide film 117 b, the titanium film 118 a, the platinum film 119 , the titanium film 120 , and the SRO film 121 , and a dielectric film formed of the PZT film 122 , and a top electrode having the SRO film 123 and the platinum film 124 .
- the top electrode film, dielectric film and bottom electrode film may be patterned by the same lithography and etching process. In this case, side surfaces of the top electrode, dielectric film and bottom electrode are positioned substantially within a same plane.
- the CVD process is used to deposit a silicon oxide film 125 all over the surface of the ferroelectric capacitor.
- the capacitor is thermally treated at a temperature of about 650° C. in an oxygen atmosphere.
- the tungsten plug 115 is prevented from being oxidized because the surface of the tungsten plug 115 is covered with the iridium film 117 a and iridium oxide film 117 b, which have an excellent oxygen barrier characteristic.
- the titanium film 118 a is formed on the iridium oxide film 117 b, it blocks the diffusion of the iridium contained in the iridium film 117 a and iridium oxide film 117 b. It is thus possible to prevent the iridium from diffusing to the SRO film 121 and the PZT film 122 through the platinum film 119 .
- a ferroelectric memory having a COP (Capacitor On Plug) structure is completed by subsequently forming a contact connected to the tungsten film 111 , drive lines and bit lines, metal interconnects, and the like.
- COP Capacitor On Plug
- FIG. 4 is a graph showing the hysteresis characteristic of a capacitor formed using a process similar to the above described process.
- FIG. 5 is a graph showing the hysteresis characteristic of a capacitor according to a comparative example. The axis of abscissa indicates a voltage applied to the capacitor, while the axis of ordinate indicates the polarization of the capacitor.
- the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 1.5 nm), an SRO film (thickness: 2.5 nm), a PZT film (Pb(Zr 0.3 Ti 0.7 )O 3 film, thickness: 130 nm), an SRO film (thickness: 10 nm), and a platinum film (thickness: 50 nm).
- the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), an SRO film (thickness: 10 nm), a PZT film (Pb(Zr 0.3 Ti 0.7 )O 3 film, thickness: 130 nm), an SRO film (thickness: 10 nm), and a platinum film (thickness: 50 nm). That is, the capacitor according to the comparative example is not provided with any diffusion prevention film (corresponding to the titanium 118 a, shown in FIG. 3 ).
- FIG. 4 present embodiment
- FIG. 5 comparative example
- the capacitor according to the present embodiment has a markedly improved quantity of switching charges (Q SW ) and a markedly improved squareness compared to the capacitor of the comparative example. That is, the capacitor according to the present embodiment has a markedly improved hysteresis characteristic compared to the capacitor of the comparative example.
- FIG. 6 is a graph showing the relationship between an x value and the quantity of switching charges for the Pb(Zr x Ti 1-x )O 3 film (PZT film) in a sample similar to that described in FIG. 4 .
- the x value when the x value is 0.35 or more, the quantity of switching charges decreases rapidly. That is, when the x value is 0.35 or more, the capacitor characteristic is rapidly degraded. Accordingly, to obtain a favorable capacitor characteristic, it is necessary that the x value is less than 0.35 (0 ⁇ x ⁇ 0.35). Further, if the x value is 0.25 or less, it is generally difficult to form a PZT film with an excellent crystallinity or the like. Therefore, preferably, 0.25 ⁇ x ⁇ 0.35.
- FIG. 7 is a graph showing the XRD pattern of a sample according to the present embodiment.
- FIG. 8 is a graph showing the XRD pattern of a sample according to the comparative example of the present embodiment.
- the axis of abscissa indicates angle (2 ⁇ ), while the axis of ordinate indicates intensity.
- the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 1.5 nm), an SRO film (thickness: 2.5 nm), and a PZT film (Pb(Zr 0.3 Ti 0.7 )O 3 film, thickness: 130 nm).
- the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), an SRO film (thickness: 10 nm), and a PZT film (Pb(Zr 0.3 Ti 0.7 )O 3 film, thickness: 130 nm). That is, the capacitor according to the comparative example is not provided with any diffusion prevention film (corresponding to the titanium film 118 a, shown in FIG. 3 ).
- each of the PZT film and SRO film is obtained by forming an amorphous film by sputtering and then annealing the amorphous film in an oxygen atmosphere for crystallization.
- FIG. 7 present embodiment
- FIG. 8 comparative example
- the PZT film of the sample according to the comparative example has a random orientation and does not exhibit a favorable crystalliinty.
- the PZT film of the sample according to the present embodiment exhibits a ( 111 ) orientation peak and thus a very favorable crystallinity.
- the titanium film 118 a (diffusion prevention film), which acts as an effective barrier for the diffusion of the iridium, is provided between the platinum film 119 (second conductive film) and the stacked film (first conductive film) made of the iridium film 117 a and the iridium oxide film 117 b.
- the degradation of the SRO and PZT films can be prevented.
- the x value for the Pb(Zr x Ti 1-x )O 3 film (PZT film) at 0 ⁇ x ⁇ 0.35, preferably 0.25 ⁇ x ⁇ 0.35, it is possible to obtain a reliable capacitor with excellent characteristics.
- the iridium oxide film does not exhibit the ( 111 ) orientation. Accordingly, if the platinum film is formed directly on the iridium oxide film, the platinum film also does not exhibit a favorable ( 111 ) orientation. It is thus not easy to obtain an SRO film or PZT film (Pb(Zr x Ti 1-x )O 3 film, 0.25 ⁇ x ⁇ 0.35) having a favorable ( 111 ) orientation.
- the titanium film is formed between the iridium oxide film and the platinum film. This allows the platinum film to be easily ( 111 ) oriented, thus making it possible to obtain SRO and PZT films having a favorable ( 111 ) orientation. It is therefore possible to obtain favorable SRO and PZT films and thus a reliable capacitor with excellent characteristics.
- FIG. 9 is a sectional view schematically showing a method of manufacturing a semiconductor device according to a second embodiment of the present invention. The steps executed before the steps of forming a capacitor are similar to those shown in FIGS. 1 and 2 for the first embodiment.
- the titanium film 116 of thickness about 10 nm is deposited by the sputtering process as shown in FIG. 9 .
- the iridium (Ir) film 117 a of about 100 nm thickness and the iridium oxide (IrO 2 ) film 117 b of about 50 nm thickness are sequentially deposited by the sputtering process.
- a titanium (Ti) film of thickness about 2.5 nm is deposited by the sputtering process.
- the titanium film is oxidized by RTA in an oxygen atmosphere to form the titanium oxide film (TiO 2 film) 118 b as a diffusion prevention film.
- the titanium oxide film 118 b prevents the upward diffusion of the iridium contained in the iridium film 117 a and iridium oxide film 117 b.
- the platinum (Pt) film 119 of thickness about 50 nm is deposited by the sputtering process.
- the titanium film 120 of about 1.5 nm thickness is deposited by the sputtering process.
- the SrRuO 3 film (SRO film) 121 of thickness about 2.5 nm is deposited on the titanium film 120 by the sputtering process. Subsequently, the SRO film 121 is crystallized by RTA in an oxygen atmosphere.
- the SRO film 121 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C.
- the Pb(Zr x Ti 1-x )O 3 film (PZT film) 122 having a thickness of about 130 nm is formed by the sputtering process. Moreover, the PZT film 122 is crystallized by RTA in an oxygen atmosphere. In the present embodiment, the value of x is 0.30. That is, as the PZT film 122 , a Pb(Zr 0.3 Ti 0.7 )O 3 film is formed.
- the SRO film 123 having a thickness of about 10 nm is deposited by the sputtering process. Moreover, the SRO film 123 is crystallized by RTA in an oxygen atmosphere. The SRO film 123 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. Furthermore, the platinum film 124 of thickness about 50 nm is deposited by the sputtering process.
- the CVD process is used to deposit a silicon oxide film (not shown) all over the surface of the resulting structure.
- the photo lithography process and the RIE process are used to pattern the silicon oxide film.
- the patterned silicon oxide film is used as a mask to etch the platinum film 124 , the SRO film 123 , and the PZT film 122 by the RIE process.
- the photo lithography process and the RIE process are used to pattern the SRO film 121 , the titanium film 120 , the platinum film 119 , the titanium oxide film 118 b, the iridium oxide film 117 b, the iridium film 117 a, and the titanium film 116 .
- a ferroelectric capacitor which comprises a bottom electrode having the titanium film 116 , the iridium film 117 a, the iridium oxide film 117 b, the titanium oxide film 118 b, the platinum film 119 , the titanium film 120 , and the SRO film 121 , a dielectric film formed of the PZT film 122 , and a top electrode having the SRO film 123 and the platinum film 124 .
- the CVD process is used to deposit the silicon oxide film 125 all over the surface of the ferroelectric capacitor.
- the capacitor is thermally treated at a temperature of about 650° C. in an oxygen atmosphere.
- the tungsten plug 115 is prevented from being oxidized because the surface of the tungsten plug 115 is covered with the iridium film 117 a and iridium oxide film 117 b, which have an excellent oxygen barrier characteristic.
- the titanium oxide film 118 b is formed on the iridium oxide film 117 b, it blocks the diffusion of the iridium contained in the iridium film 117 a and iridium oxide film 117 b. It is thus possible to prevent the iridium from diffusing to the SRO film 121 and the PZT film 122 through the platinum film 119 .
- a ferroelectric memory having the COP structure is completed by subsequently forming a contact connected to the tungsten film 111 , drive lines and bit lines, metal interconnects, and the like.
- the titanium oxide film 118 b is provided between the platinum film 119 (second conductive film) and the stacked film (first conductive film) made of the iridium film 117 a and the iridium oxide film 117 b.
- the relationship between the x value and the quantity of switching charges for the Pb(Zr x Ti 1-x )O 3 film (PZT film) exhibits a tendency similar to that shown in FIG. 6 . Accordingly, as in the case of the first embodiment, by setting the x value for the PZT film at 0 ⁇ x ⁇ 0.35, preferably 0.25 ⁇ x ⁇ 0.35, it is possible to obtain a reliable capacitor with excellent characteristics.
- the diffusion prevention film that prevents the diffusion of the iridium may be a metal film containing at least one of Ti, V, W, Zr, Co, Mg, Hf, Mo, Mn, Ta, Nb, Pb, and Al.
- it may be a metal oxide film containing at least one of Ti, V, W, Zr, Co, Mg, Hf, Mo, Mn, Ta, Nb, Pb, Al, and Ru.
- it may be a stacked film of the above metal film and metal oxide film.
- the metal oxide film may typically be a TiO 2 film, a ZrO 2 film, a CoO 2 film, PbO 2 film, Al 2 O 3 film, an SRO film, an Sr(Ru,Ti)O 3 film, or the like.
- the stacked film of the metal film and metal oxide film may typically be a Ti/SRO film, a Ti/Sr(Ru,Ti)O 3 film, a Co/SRO film, a Co/Sr(Ru,Ti)O 3 film, or the like.
- the effect of the SRO film or Sr(Ru,Ti)O 3 film in suppressing the diffusion of iridium is mainly based on the reaction of iridium with the SRO film or Sr(Ru,Ti)O 3 film.
- the iridium upon reacting with the SRO film or Sr(Ru,Ti)O 3 film, the iridium is consumed and thus prevented from diffusing upward.
- the reaction with the iridium may degrade the crystallinity of the SRO film or Sr(Ru,Ti)O 3 film.
- the SRO film or Sr(Ru,Ti)O 3 film, used as a diffusion prevention film does not contact with the PZT film. Consequently, the degraded crystallinity does not substantially affect the PZT film or the like.
- the first conductive film may be a single film of iridium (Ir), a single film of iridium oxide (IrO 2 ), or a stacked film of the iridium film and iridium oxide film.
- the second conductive film may be a noble metal film including at least one of a platinum film and a ruthenium film.
- the third conductive film may be a conductive metal oxide film having a perovskite crystal structure (general formula: ABO 3 ) and containing at least one of Ru, Co, and Ni.
- the third conductive film may be an SrRuO 3 film, a (La,Sr)CoO 3 film, a BaRuO 3 film, an LaNiO 3 film, or the like.
- the dielectric film may be an insulating metal oxide film having a perovskite structure expressed by A(Zr x Ti 1-x )O 3 (A denotes at least one A site element, 0 ⁇ x ⁇ 0.35, preferably 0.25 ⁇ x ⁇ 0.35).
- A denotes at least one A site element, 0 ⁇ x ⁇ 0.35, preferably 0.25 ⁇ x ⁇ 0.35).
- an insulating metal oxide film containing Pb as an A site element is desirably used.
- the insulating metal oxide film may typically be a Pb(Zr x Ti 1-x )O 3 film (PZT film), a (Pb,La) (Zr x Ti 1-x )O 3 film, or the like.
- the plug may be a tungsten plug or a polysilicon plug.
- the diffusion prevention film, the first conductive film, the second conductive film, the third conductive film, and the dielectric film may be formed using the sputtering process, the CVD process, or a sol-gel process.
- the structure described in the foregoing embodiments can be applicable to a series connected TC unit type ferroelectric memory, which includes series connected memory cells each having a transistor having a source terminal and a drain terminal and a ferroelectric capacitor between the two terminals.
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Abstract
Description
- This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2004-337654, filed Nov. 22, 2004, the entire contents of which are incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates to a semiconductor device having a capacitor.
- 2. Description of the Related Art
- In recent years, many efforts have been made to develop ferroelectric memories using a ferroelectric film as a dielectric film of a capacitor, that is, FeRAMs (Ferroelectric Random Access Memories). A typical ferroelectric film used for a ferroelectric memory is a Pb(ZrxTi1-x)O3 film (PZT film) having a perovskite structure.
- If a PZT film is used as a ferroelectric film, electrodes are composed of conductive perovskite type metal oxide films such as SrRuO3 films (SRO films) or the like in order to, for example, improve their fatigue characteristic. For example, Jpn. Pat. Appln. KOKAI Publication No. 2000-208725 and Jpn. Pat. Appln. KOKAI Publication No. 2000-260954 describe ferroelectric capacitors having electrodes each made of a stacked film composed of an SRO film and a Pt film.
- Further, what is called a COP (Capacitor On Plug) structure has been proposed in which a capacitor is formed on a plug in order to increase the degree of integration of the ferroelectric memory. In the COP structure, to prevent the plug from being oxidized by thermal treatment, a bottom electrode of the capacitor is partly composed of an Ir film or Ir oxide film, which has an excellent oxygen barrier characteristic.
- However, with this structure, Ir disadvantageously diffuses through the conductive perovskite type metal oxide film or a capacitor dielectric film, which degrades the characteristics or reliability of the capacitor. For example, Ir may react with Pb in the PZT film to form a conductive oxide, which increases a leak current of the capacitor or Ir may react with Sr in the SRO film to degrade the crystallinity of the SRO film, which degrades the characteristics or reliability of a dielectric film on the SRO film.
- Thus, a problem with a capacitor having a capacitor dielectric film made of a metal oxide film having a perovskite structure is that the diffusion of Ir may degrade the characteristics or reliability of the capacitor.
- According to an aspect of the present invention, there is provided a semiconductor device comprising a capacitor provided above the semiconductor substrate and including a bottom electrode, a top electrode, and a dielectric film provided between the bottom electrode and the top electrode, the bottom electrode comprising a first conductive film containing iridium, a second conductive film provided between the dielectric film and the first conductive film and formed of a noble metal film, a third conductive film provided between the dielectric film and the second conductive film and formed of a conductive metal oxide film having a perovskite structure, and a diffusion prevention film provided between the first conductive film and the second conductive film and including at least one of a metal film and a metal oxide film, the diffusion prevention film preventing diffusion of iridium contained in the first conductive film, and the dielectric film including an insulating metal oxide film having a perovskite structure, the insulating metal oxide film being expressed by A(ZrxTi1-x)O3 (A is at least one A site element, 0<x<0.35).
- FIGS. 1 to 3 are sectional views schematically showing a method of manufacturing a semiconductor device according to a first embodiment of the present invention;
-
FIG. 4 is a graph showing a hysteresis characteristic of a capacitor according to the first embodiment of the present invention; -
FIG. 5 is a graph showing a hysteresis characteristic of a capacitor according to a comparative example of the first embodiment of the present invention; -
FIG. 6 is a graph showing the relationship between an x value and the quantity of switching charges for a Pb(ZrxTi1-x)O3 film (PZT film) according to the first embodiment of the present invention; -
FIG. 7 is a graph showing the intensity of an XRD pattern according to the first embodiment of the present invention; -
FIG. 8 is a graph showing the intensity of the XRD pattern according to a comparative example of the first embodiment of the present invention; and -
FIG. 9 is a sectional view schematically showing a method of manufacturing a semiconductor device according to a second embodiment of the present invention. - Embodiments of the present invention will be described below with reference to the drawings.
- FIGS. 1 to 3 are sectional views schematically showing a method of manufacturing a semiconductor device according to a first embodiment of the present invention.
- First, as shown in
FIG. 1 , anisolation region 101 of an STI (Shallow Trench Isolation) structure is formed on a p-type silicon substrate (semiconductor substrate) 100. Subsequently, an MIS transistor is formed as described below. - First, as a gate
insulating film 102, a silicon oxide film of thickness about 6 nm is formed by thermal oxidization. Subsequently, arsenic-doped n+type polysilicon film 103 is formed on thegate insulating film 102. Moreover, a WSixfilm 104 and asilicon nitride film 105 are formed on thepolysilicon film 103. Subsequently, thepolysilicon film 103, the WSixfilm 104, and thesilicon nitride film 105 are processed by a normal photo lithography process and a normal RIE process to form a gate electrode. Subsequently, asilicon nitride film 106 is deposited all over the surface of the resulting structure. Moreover, RIE is carried out to form side wall spacers formed of thesilicon nitride film 106, on side walls of the gate electrode. Although not described in detail, in the present step, source/drain regions 107 are formed by ion implantation and thermal treatment. - Then, as shown in
FIG. 2 , a CVD (Chemical Vapor Deposition) process is used to deposit asilicon oxide film 108 all over the surface of the resulting structure. Further, a CMP process is used to execute a flattening process. Subsequently, a contact hole is formed through thesilicon oxide film 108 so as to reach one of the source/drain regions 107. Then, a sputtering process or the CVD process is used to deposit a titanium film. Subsequently, the titanium film is nitrided by thermal treatment in a foaming gas to form aTiN film 110. Moreover, the CVD process is used to deposit atungsten film 111. Subsequently, the CMP process is used to remove theTiN film 110 andtungsten film 111 from outside the contact hole, while leaving the TiNfilm 110 and thetungsten film 111 in the contact hole. This forms a plug connected to one of the source/drain regions 107. Then, the CVD process is used to deposit asilicon nitride film 112 all over the surface of the resulting structure. Furthermore, a control hole is formed so as to reach the other source/drain region 107. Subsequently, a method similar to that described above is used to form aTiN film 114 and atungsten film 115 in the contact hole. This forms a plug connected to the other source/drain region 107. - Then, as shown in
FIG. 3 , a titanium (Ti)film 116 of thickness about 10 nm is deposited by the sputtering process. Subsequently, as a firstconductive film 117, an iridium (Ir)film 117 a of about 100 nm thickness and an iridium oxide (IrO2)film 117 b of about 50 nm thickness are sequentially deposited by the sputtering process. Theiridium film 117 a and theiridium oxide film 117 b have an excellent oxygen barrier characteristic and can thus prevent the oxidization of theplug 115 during the subsequent thermal treatment step. Subsequently, as a diffusion prevention film, a titanium (Ti)film 118 a of thickness about 2.5 nm is deposited by the sputtering process. Thetitanium film 118 a prevents the upward diffusion of the iridium contained in theiridium film 117 a andiridium oxide film 117 b. Subsequently, as a second conductive film, a platinum (Pt)film 119 of thickness about 50 nm is deposited by the sputtering process. Then, as a seed layer, atitanium film 120 of about 1.5 nm thickness is deposited by the sputtering process. Moreover, as a third conductive film, an SrRuO3 film (SRO film) 121 of thickness about 2.5 nm is deposited on thetitanium film 120 by the sputtering process. Subsequently, theSRO film 121 is crystallized by RTA (Rapid Thermal Annealing) in an oxygen atmosphere. TheSRO film 121 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. - Then, as a dielectric film (ferroelectric film) of the capacitor, a Pb(ZrxTi1-x)O3 film (PZT film) 122 having a thickness of about 130 nm is formed by the sputtering process. Moreover, the
PZT film 122 is crystallized by RTA in an oxygen atmosphere. In the present embodiment, the value of x is 0.30. That is, as thePZT film 122, a Pb(Zr0.3Ti0.7)O3 film is formed. - Then, an
SRO film 123 having a thickness of about 10 nm is deposited by the sputtering process. Moreover, theSRO film 123 is crystallized by RTA in an oxygen atmosphere. TheSRO film 123 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. Furthermore, aplatinum film 124 of thickness about 50 nm is deposited by the sputtering process. - Then, the CVD process is used to deposit a silicon oxide film (not shown) all over the surface of the resulting structure. Moreover, the photo lithography process and the RIE process are used to pattern the silicon oxide film. Subsequently, the patterned silicon oxide film is used as a mask to etch the
platinum film 124, theSRO film 123, and thePZT film 122 by the RIE process. Furthermore, the photo lithography process and the RIE process are used to pattern theSRO film 121, thetitanium film 120, theplatinum film 119, thetitanium film 118 a, theiridium oxide film 117 b, theiridium film 117 a, and thetitanium film 116. - In this manner, a ferroelectric capacitor is formed which comprises a bottom electrode having the
titanium film 116, theiridium film 117 a, theiridium oxide film 117 b, thetitanium film 118 a, theplatinum film 119, thetitanium film 120, and theSRO film 121, and a dielectric film formed of thePZT film 122, and a top electrode having theSRO film 123 and theplatinum film 124. - In the ferroelectric capacitor forming step described above, the top electrode film, dielectric film and bottom electrode film may be patterned by the same lithography and etching process. In this case, side surfaces of the top electrode, dielectric film and bottom electrode are positioned substantially within a same plane.
- Then, the CVD process is used to deposit a
silicon oxide film 125 all over the surface of the ferroelectric capacitor. Subsequently, to recover from damage to thePZT film 122 during etching, the capacitor is thermally treated at a temperature of about 650° C. in an oxygen atmosphere. During the thermal treatment, thetungsten plug 115 is prevented from being oxidized because the surface of thetungsten plug 115 is covered with theiridium film 117 a andiridium oxide film 117 b, which have an excellent oxygen barrier characteristic. Further, since thetitanium film 118 a is formed on theiridium oxide film 117 b, it blocks the diffusion of the iridium contained in theiridium film 117 a andiridium oxide film 117 b. It is thus possible to prevent the iridium from diffusing to theSRO film 121 and thePZT film 122 through theplatinum film 119. - The subsequent steps are not shown. A ferroelectric memory having a COP (Capacitor On Plug) structure is completed by subsequently forming a contact connected to the
tungsten film 111, drive lines and bit lines, metal interconnects, and the like. -
FIG. 4 is a graph showing the hysteresis characteristic of a capacitor formed using a process similar to the above described process.FIG. 5 is a graph showing the hysteresis characteristic of a capacitor according to a comparative example. The axis of abscissa indicates a voltage applied to the capacitor, while the axis of ordinate indicates the polarization of the capacitor. - Specifically, for a sample-according to the present embodiment, the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 1.5 nm), an SRO film (thickness: 2.5 nm), a PZT film (Pb(Zr0.3Ti0.7)O3 film, thickness: 130 nm), an SRO film (thickness: 10 nm), and a platinum film (thickness: 50 nm).
- For a sample according to the comparative example of the present embodiment, the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), an SRO film (thickness: 10 nm), a PZT film (Pb(Zr0.3Ti0.7)O3 film, thickness: 130 nm), an SRO film (thickness: 10 nm), and a platinum film (thickness: 50 nm). That is, the capacitor according to the comparative example is not provided with any diffusion prevention film (corresponding to the
titanium 118 a, shown inFIG. 3 ). - Comparison of
FIG. 4 (present embodiment) withFIG. 5 (comparative example) clearly indicates that the capacitor according to the present embodiment has a markedly improved quantity of switching charges (QSW) and a markedly improved squareness compared to the capacitor of the comparative example. That is, the capacitor according to the present embodiment has a markedly improved hysteresis characteristic compared to the capacitor of the comparative example. -
FIG. 6 is a graph showing the relationship between an x value and the quantity of switching charges for the Pb(ZrxTi1-x)O3 film (PZT film) in a sample similar to that described inFIG. 4 . - As shown in
FIG. 6 , when the x value is 0.35 or more, the quantity of switching charges decreases rapidly. That is, when the x value is 0.35 or more, the capacitor characteristic is rapidly degraded. Accordingly, to obtain a favorable capacitor characteristic, it is necessary that the x value is less than 0.35 (0<x<0.35). Further, if the x value is 0.25 or less, it is generally difficult to form a PZT film with an excellent crystallinity or the like. Therefore, preferably, 0.25<x<0.35. -
FIG. 7 is a graph showing the XRD pattern of a sample according to the present embodiment.FIG. 8 is a graph showing the XRD pattern of a sample according to the comparative example of the present embodiment. The axis of abscissa indicates angle (2θ), while the axis of ordinate indicates intensity. - For the sample according to the present embodiment, the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 1.5 nm), an SRO film (thickness: 2.5 nm), and a PZT film (Pb(Zr0.3Ti0.7)O3 film, thickness: 130 nm).
- For the sample according to the comparative example, the following films are sequentially formed on a silicon oxide film on a silicon substrate: a titanium film (thickness: 10 nm), an iridium film (thickness: 100 nm), an iridium oxide film (thickness: 50 nm), a platinum film (thickness: 50 nm), a titanium film (thickness: 2.5 nm), an SRO film (thickness: 10 nm), and a PZT film (Pb(Zr0.3Ti0.7)O3 film, thickness: 130 nm). That is, the capacitor according to the comparative example is not provided with any diffusion prevention film (corresponding to the
titanium film 118 a, shown inFIG. 3 ). - For both samples according to the present embodiment and the comparative example, respectively, each of the PZT film and SRO film is obtained by forming an amorphous film by sputtering and then annealing the amorphous film in an oxygen atmosphere for crystallization.
- Comparison of
FIG. 7 (present embodiment) withFIG. 8 (comparative example) clearly indicates that the PZT film of the sample according to the comparative example has a random orientation and does not exhibit a favorable crystalliinty. In contrast, the PZT film of the sample according to the present embodiment exhibits a (111) orientation peak and thus a very favorable crystallinity. - As described above, according to the present embodiment, the
titanium film 118 a (diffusion prevention film), which acts as an effective barrier for the diffusion of the iridium, is provided between the platinum film 119 (second conductive film) and the stacked film (first conductive film) made of theiridium film 117 a and theiridium oxide film 117 b. This makes it possible to prevent the iridium from diffusing to the SRO film 121 (third conductive film) and PZT film 122 (dielectric film) through theplatinum film 119. It is in turn possible to suppress the reaction of the iridium with elements contained in the SRO film or the reaction of the iridium with elements contained in the PZT film. Consequently, the degradation of the SRO and PZT films can be prevented. In particular, by setting the x value for the Pb(ZrxTi1-x)O3 film (PZT film) at 0<x<0.35, preferably 0.25<x<0.35, it is possible to obtain a reliable capacitor with excellent characteristics. - In general, the iridium oxide film does not exhibit the (111) orientation. Accordingly, if the platinum film is formed directly on the iridium oxide film, the platinum film also does not exhibit a favorable (111) orientation. It is thus not easy to obtain an SRO film or PZT film (Pb(ZrxTi1-x)O3 film, 0.25<x<0.35) having a favorable (111) orientation. In the present embodiment, the titanium film is formed between the iridium oxide film and the platinum film. This allows the platinum film to be easily (111) oriented, thus making it possible to obtain SRO and PZT films having a favorable (111) orientation. It is therefore possible to obtain favorable SRO and PZT films and thus a reliable capacitor with excellent characteristics.
-
FIG. 9 is a sectional view schematically showing a method of manufacturing a semiconductor device according to a second embodiment of the present invention. The steps executed before the steps of forming a capacitor are similar to those shown inFIGS. 1 and 2 for the first embodiment. - After the step shown in
FIG. 2 for the first embodiment, thetitanium film 116 of thickness about 10 nm is deposited by the sputtering process as shown inFIG. 9 . Subsequently, as the firstconductive film 117, the iridium (Ir)film 117 a of about 100 nm thickness and the iridium oxide (IrO2)film 117 b of about 50 nm thickness are sequentially deposited by the sputtering process. Subsequently, a titanium (Ti) film of thickness about 2.5 nm is deposited by the sputtering process. Moreover, the titanium film is oxidized by RTA in an oxygen atmosphere to form the titanium oxide film (TiO2 film) 118 b as a diffusion prevention film. Thetitanium oxide film 118 b prevents the upward diffusion of the iridium contained in theiridium film 117 a andiridium oxide film 117 b. Subsequently, as a second conductive film, the platinum (Pt)film 119 of thickness about 50 nm is deposited by the sputtering process. Then, as a seed layer, thetitanium film 120 of about 1.5 nm thickness is deposited by the sputtering process. Moreover, as a third conductive film, the SrRuO3 film (SRO film) 121 of thickness about 2.5 nm is deposited on thetitanium film 120 by the sputtering process. Subsequently, theSRO film 121 is crystallized by RTA in an oxygen atmosphere. TheSRO film 121 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. - Then, as a dielectric film (ferroelectric film) of the capacitor, the Pb(ZrxTi1-x)O3 film (PZT film) 122 having a thickness of about 130 nm is formed by the sputtering process. Moreover, the
PZT film 122 is crystallized by RTA in an oxygen atmosphere. In the present embodiment, the value of x is 0.30. That is, as thePZT film 122, a Pb(Zr0.3Ti0.7)O3 film is formed. - Then, the
SRO film 123 having a thickness of about 10 nm is deposited by the sputtering process. Moreover, theSRO film 123 is crystallized by RTA in an oxygen atmosphere. TheSRO film 123 with an excellent crystallinity can be easily formed by depositing the film at a temperature of, for example, 500° C. Furthermore, theplatinum film 124 of thickness about 50 nm is deposited by the sputtering process. - Then, the CVD process is used to deposit a silicon oxide film (not shown) all over the surface of the resulting structure. Moreover, the photo lithography process and the RIE process are used to pattern the silicon oxide film. Subsequently, the patterned silicon oxide film is used as a mask to etch the
platinum film 124, theSRO film 123, and thePZT film 122 by the RIE process. Furthermore, the photo lithography process and the RIE process are used to pattern theSRO film 121, thetitanium film 120, theplatinum film 119, thetitanium oxide film 118 b, theiridium oxide film 117 b, theiridium film 117 a, and thetitanium film 116. - In this manner, a ferroelectric capacitor is formed which comprises a bottom electrode having the
titanium film 116, theiridium film 117 a, theiridium oxide film 117 b, thetitanium oxide film 118 b, theplatinum film 119, thetitanium film 120, and theSRO film 121, a dielectric film formed of thePZT film 122, and a top electrode having theSRO film 123 and theplatinum film 124. - Then, the CVD process is used to deposit the
silicon oxide film 125 all over the surface of the ferroelectric capacitor. Subsequently, to recover from damage done to thePZT film 122 during etching, the capacitor is thermally treated at a temperature of about 650° C. in an oxygen atmosphere. During the thermal treatment, thetungsten plug 115 is prevented from being oxidized because the surface of thetungsten plug 115 is covered with theiridium film 117 a andiridium oxide film 117 b, which have an excellent oxygen barrier characteristic. Further, since thetitanium oxide film 118 b is formed on theiridium oxide film 117 b, it blocks the diffusion of the iridium contained in theiridium film 117 a andiridium oxide film 117 b. It is thus possible to prevent the iridium from diffusing to theSRO film 121 and thePZT film 122 through theplatinum film 119. - The subsequent steps are not shown. A ferroelectric memory having the COP structure is completed by subsequently forming a contact connected to the
tungsten film 111, drive lines and bit lines, metal interconnects, and the like. - As described above, according to the present embodiment, the
titanium oxide film 118 b is provided between the platinum film 119 (second conductive film) and the stacked film (first conductive film) made of theiridium film 117 a and theiridium oxide film 117 b. Thus, as in the case of the first embodiment, it is possible to obtain favorable SRO and PZT films and thus a reliable capacitor with excellent characteristics. Also in the present embodiment, the relationship between the x value and the quantity of switching charges for the Pb(ZrxTi1-x)O3 film (PZT film) exhibits a tendency similar to that shown inFIG. 6 . Accordingly, as in the case of the first embodiment, by setting the x value for the PZT film at 0<x<0.35, preferably 0.25<x<0.35, it is possible to obtain a reliable capacitor with excellent characteristics. - Various changes may be made to the above first and second embodiments as described below.
- The diffusion prevention film that prevents the diffusion of the iridium may be a metal film containing at least one of Ti, V, W, Zr, Co, Mg, Hf, Mo, Mn, Ta, Nb, Pb, and Al. Alternatively, it may be a metal oxide film containing at least one of Ti, V, W, Zr, Co, Mg, Hf, Mo, Mn, Ta, Nb, Pb, Al, and Ru. Alternatively, it may be a stacked film of the above metal film and metal oxide film. The metal oxide film may typically be a TiO2 film, a ZrO2 film, a CoO2 film, PbO2 film, Al2O3 film, an SRO film, an Sr(Ru,Ti)O3 film, or the like. The stacked film of the metal film and metal oxide film may typically be a Ti/SRO film, a Ti/Sr(Ru,Ti)O3 film, a Co/SRO film, a Co/Sr(Ru,Ti)O3 film, or the like. The effect of the SRO film or Sr(Ru,Ti)O3 film in suppressing the diffusion of iridium is mainly based on the reaction of iridium with the SRO film or Sr(Ru,Ti)O3 film. Specifically, upon reacting with the SRO film or Sr(Ru,Ti)O3 film, the iridium is consumed and thus prevented from diffusing upward. The reaction with the iridium may degrade the crystallinity of the SRO film or Sr(Ru,Ti)O3 film. However, the SRO film or Sr(Ru,Ti)O3 film, used as a diffusion prevention film, does not contact with the PZT film. Consequently, the degraded crystallinity does not substantially affect the PZT film or the like.
- The first conductive film may be a single film of iridium (Ir), a single film of iridium oxide (IrO2), or a stacked film of the iridium film and iridium oxide film.
- The second conductive film may be a noble metal film including at least one of a platinum film and a ruthenium film.
- The third conductive film may be a conductive metal oxide film having a perovskite crystal structure (general formula: ABO3) and containing at least one of Ru, Co, and Ni. Typically, the third conductive film may be an SrRuO3 film, a (La,Sr)CoO3 film, a BaRuO3 film, an LaNiO3 film, or the like.
- The dielectric film may be an insulating metal oxide film having a perovskite structure expressed by A(ZrxTi1-x)O3 (A denotes at least one A site element, 0<x<0.35, preferably 0.25<x<0.35). In particular, an insulating metal oxide film containing Pb as an A site element is desirably used. The insulating metal oxide film may typically be a Pb(ZrxTi1-x)O3 film (PZT film), a (Pb,La) (ZrxTi1-x)O3 film, or the like.
- The plug may be a tungsten plug or a polysilicon plug.
- The diffusion prevention film, the first conductive film, the second conductive film, the third conductive film, and the dielectric film may be formed using the sputtering process, the CVD process, or a sol-gel process.
- The structure described in the foregoing embodiments can be applicable to a series connected TC unit type ferroelectric memory, which includes series connected memory cells each having a transistor having a source terminal and a drain terminal and a ferroelectric capacitor between the two terminals.
- Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Claims (11)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090061538A1 (en) * | 2007-08-16 | 2009-03-05 | Samsung Electronics Co., Ltd. | Methods of forming ferroelectric capacitors and methods of manufacturing semiconductor devices using the same |
| US8733906B2 (en) | 2011-09-16 | 2014-05-27 | Ricoh Company, Ltd. | Electromechanical conversion element, liquid drop ejection head, liquid drop ejection device, and image forming apparatus |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208372B2 (en) * | 2005-01-19 | 2007-04-24 | Sharp Laboratories Of America, Inc. | Non-volatile memory resistor cell with nanotip electrode |
| KR100718267B1 (en) * | 2005-03-23 | 2007-05-14 | 삼성전자주식회사 | Ferroelectric structure, method for manufacturing same, semiconductor device including same and method for manufacturing same |
| JP6273829B2 (en) | 2013-09-13 | 2018-02-07 | 株式会社リコー | ELECTRO-MACHINE CONVERSION ELEMENT AND MANUFACTURING METHOD THEREOF, AND LIQUID DISCHARGE HEAD HAVING ELECTRO-MECHANICAL CONVERSION ELEMENT, AND LIQUID DISCHARGE EJECTION DEVICE HAVING LIQUID DISCHARGE HEAD |
| JP7189848B2 (en) * | 2019-08-07 | 2022-12-14 | 株式会社東芝 | Semiconductor device and its manufacturing method |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010015448A1 (en) * | 1999-12-28 | 2001-08-23 | Takashi Kawakubo | Ferroelectric capacitor and semiconductor device |
| US6351006B1 (en) * | 1998-11-10 | 2002-02-26 | Kabushiki Kaisha Toshiba | Ferroelectric capacitor with means to prevent deterioration |
| US6479849B1 (en) * | 1999-06-02 | 2002-11-12 | Sony Corporation | Dielectric capacitor and memory and method of manufacturing the same |
| US20030119273A1 (en) * | 2001-12-21 | 2003-06-26 | Sanjeev Aggarwal | Methods of preventing reduction of irox during pzt formation by metalorganic chemical vapor deposition or other processing |
| US20030127674A1 (en) * | 2000-08-31 | 2003-07-10 | Ramamoorthy Ramesh | Conductively doped strontium titanate barrier intermediate a silicon underlayer and an epitaxial metal oxide film |
| US20030143853A1 (en) * | 2002-01-31 | 2003-07-31 | Celii Francis G. | FeRAM capacitor stack etch |
| US6693791B2 (en) * | 1995-07-07 | 2004-02-17 | Rohm Co., Ltd. | Ferroelectric capacitor and a method for manufacturing thereof |
| US20040155278A1 (en) * | 2003-02-10 | 2004-08-12 | Katsuaki Natori | Semiconductor device, apparatus and method for manufacturing the same |
| US20040217404A1 (en) * | 2003-05-02 | 2004-11-04 | Hiroshi Itokawa | Semiconductor device |
| US20050001251A1 (en) * | 2003-05-07 | 2005-01-06 | Hiroshi Itokawa | Semiconductor device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11220095A (en) | 1998-01-30 | 1999-08-10 | Sony Corp | Method for manufacturing dielectric capacitor |
| JP3745553B2 (en) | 1999-03-04 | 2006-02-15 | 富士通株式会社 | Ferroelectric capacitor and method for manufacturing semiconductor device |
-
2004
- 2004-11-22 JP JP2004337654A patent/JP4220459B2/en not_active Expired - Fee Related
- 2004-12-30 US US11/024,422 patent/US7049650B1/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6693791B2 (en) * | 1995-07-07 | 2004-02-17 | Rohm Co., Ltd. | Ferroelectric capacitor and a method for manufacturing thereof |
| US6351006B1 (en) * | 1998-11-10 | 2002-02-26 | Kabushiki Kaisha Toshiba | Ferroelectric capacitor with means to prevent deterioration |
| US6479849B1 (en) * | 1999-06-02 | 2002-11-12 | Sony Corporation | Dielectric capacitor and memory and method of manufacturing the same |
| US20010015448A1 (en) * | 1999-12-28 | 2001-08-23 | Takashi Kawakubo | Ferroelectric capacitor and semiconductor device |
| US20030127674A1 (en) * | 2000-08-31 | 2003-07-10 | Ramamoorthy Ramesh | Conductively doped strontium titanate barrier intermediate a silicon underlayer and an epitaxial metal oxide film |
| US20030119273A1 (en) * | 2001-12-21 | 2003-06-26 | Sanjeev Aggarwal | Methods of preventing reduction of irox during pzt formation by metalorganic chemical vapor deposition or other processing |
| US20030143853A1 (en) * | 2002-01-31 | 2003-07-31 | Celii Francis G. | FeRAM capacitor stack etch |
| US20040155278A1 (en) * | 2003-02-10 | 2004-08-12 | Katsuaki Natori | Semiconductor device, apparatus and method for manufacturing the same |
| US20040217404A1 (en) * | 2003-05-02 | 2004-11-04 | Hiroshi Itokawa | Semiconductor device |
| US6924519B2 (en) * | 2003-05-02 | 2005-08-02 | Kabushiki Kaisha Toshiba | Semiconductor device with perovskite capacitor |
| US20050001251A1 (en) * | 2003-05-07 | 2005-01-06 | Hiroshi Itokawa | Semiconductor device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090061538A1 (en) * | 2007-08-16 | 2009-03-05 | Samsung Electronics Co., Ltd. | Methods of forming ferroelectric capacitors and methods of manufacturing semiconductor devices using the same |
| US8733906B2 (en) | 2011-09-16 | 2014-05-27 | Ricoh Company, Ltd. | Electromechanical conversion element, liquid drop ejection head, liquid drop ejection device, and image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006147935A (en) | 2006-06-08 |
| US7049650B1 (en) | 2006-05-23 |
| JP4220459B2 (en) | 2009-02-04 |
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