US20020142536A1 - Method of making single c-axis PGO thin film on ZrO2 for non-volatile memory applications - Google Patents
Method of making single c-axis PGO thin film on ZrO2 for non-volatile memory applications Download PDFInfo
- Publication number
- US20020142536A1 US20020142536A1 US10/128,604 US12860402A US2002142536A1 US 20020142536 A1 US20020142536 A1 US 20020142536A1 US 12860402 A US12860402 A US 12860402A US 2002142536 A1 US2002142536 A1 US 2002142536A1
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- Prior art keywords
- pgo
- layer
- oxide
- insulator
- film
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title 2
- 239000010408 film Substances 0.000 claims abstract description 47
- 239000012212 insulator Substances 0.000 claims abstract description 46
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 31
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 238000010897 surface acoustic wave method Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910018516 Al—O Inorganic materials 0.000 claims description 9
- 238000005240 physical vapour deposition Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910003077 Ti−O Inorganic materials 0.000 claims description 6
- 238000000224 chemical solution deposition Methods 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 230000005669 field effect Effects 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000608 laser ablation Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- REDNGDDUEDWIQI-UHFFFAOYSA-N [O].[Ta].[Ir] Chemical compound [O].[Ta].[Ir] REDNGDDUEDWIQI-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- XKENYNILAAWPFQ-UHFFFAOYSA-N dioxido(oxo)germane;lead(2+) Chemical compound [Pb+2].[O-][Ge]([O-])=O XKENYNILAAWPFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- PKLMYPSYVKAPOX-UHFFFAOYSA-N tetra(propan-2-yloxy)germane Chemical compound CC(C)O[Ge](OC(C)C)(OC(C)C)OC(C)C PKLMYPSYVKAPOX-UHFFFAOYSA-N 0.000 description 1
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- H01L28/56—Capacitors with a dielectric comprising a perovskite structure material the dielectric comprising two or more layers, e.g. comprising buffer layers, seed layers, gradient layers
Definitions
- This invention relates to a single c-axis Lead Germanium Oxide (PGO) thin film on an insulator layer for non-volatile memory applications and methods of making the same and, more particularly, to a PGO thin film on a Zirconium Oxide (ZrO 2 ) insulator for ferroelectric random access memory (FeRAM) and dynamic random access memory (DRAM) applications.
- PGO Lead Germanium Oxide
- ZrO 2 Zirconium Oxide
- FeRAM ferroelectric random access memory
- DRAM dynamic random access memory
- PGO Lead Germanium Oxide
- Pb 5 Ge 3 O 11 is a well-known ferroelectric material. Pure c-axis oriented PGO thin films have been successfully grown on Iridium (Ir), Platinum (Pt), Platinum/Iridium (Pt/Ir) and Iridium-Tantalum-Oxygen (Ir—Ta—O) conductive electrodes. These structures can be used for metal ferroelectric metal oxide semiconductor (MFMOS) single transistor memory applications.
- MMOS metal ferroelectric metal oxide semiconductor
- Ferroelectric devices have also been manufactured with SrBi 2 Ta 2 O 9 (SBT). Unlike the ferroelectric material SBT, which exhibits ferroelectric properties with a polycrystalline structure, PGO only exhibits ferroelectric properties when it is c-axis oriented. However, it is rather difficult to grow single-phase c-axis PGO films on insulators because PGO films usually exhibit amorphous or polycrystalline structure.
- SBT SrBi 2 Ta 2 O 9
- Metal ferroelectric semiconductor field effect transistors are an attractive alternative to MFMOS.
- MFSFET Metal ferroelectric semiconductor field effect transistors
- a strong interaction between the PGO film and the Silicon precludes the fabrication of such devices using a PGO ferroelectric layer.
- Metal ferroelectric insulator semiconductor field effect transistors have also been investigated because their structure is simpler than that of MFMOS structures.
- good insulator films for fabrication of MFISFET devices which include a PGO ferroelectric layer, have not been found. Accordingly, there is a need for finding a good insulator film that allows for the fabrication of MFISFET devices having a PGO ferroelectric layer.
- the invention comprises a new thin film structure, including a single-phase c-axis PGO film on an insulator, such as ZrO 2 , for metal ferroelectric insulator semiconductor single transistor non-volatile memory applications.
- This PGO-on-insulator structure can also be used in capacitors, pyroelectric infrared sensors, optical displays, optical switches, piezoelectric transducers, and surface acoustic wave devices.
- an object of the invention is to provide a MFIS transistor structure including a PGO ferroelectric film.
- Another object of the invention is to provide a MFIS transistor structure including a ZrO 2 insulator film.
- a further object of the invention is to provide a MFIS transistor structure including a PGO ferroelectric layer on an insulator layer.
- FIG. 1 is a schematic of the inventive PGO ferroelectric film on an insulator film.
- FIG. 2 is a graph of an X-ray diffraction spectrum of a PGO film on a ZrO 2 insulator film.
- FIG. 3 is a graph of a high frequency Capacitance-Voltage (CV) measurement of a metal ferroelectric insulator semiconductor (MFIS) capacitor comprising Pt/PGO/ZrO 2 /Si.
- CV Capacitance-Voltage
- FIG. 4 is a graph of a Capacitance-Voltage (CV) measurement of a Pt/PGO(180 nm)/Ir capacitor structure.
- FIG. 5 is a graph of a leakage current (I-V) of a PGO/ZrO 2 film.
- FIG. 6 is a schematic of a metal ferroelectric insulator semiconductor field effect transistor including a PGO layer on an insulator structure.
- FIG. 7 is a flowchart of the method of making the PGO-on-insulator structure of the present invention.
- FIG. 1 shows a schematic of the inventive device.
- Device 10 includes a Semiconductor substrate 12 such as a Silicon substrate.
- An Insulator film 14 such as ZrO 2 , is positioned on substrate 12 .
- a ferroelectric layer 16 namely, a substantially single phase, c-axis Pb 5 Ge 3 O 11 (PGO) film, is positioned on insulator film 14 .
- a metal top electrode 18 is positioned on PGO film 16 .
- a typical method for preparing such a structure may include the following steps.
- Third, the PGO film is deposited by any of the following methods: spin-on; physical vapor deposition; CVD; metal organic CVD (MOCVD); chemical solution deposition (CSD); and laser ablation.
- the following device was manufactured.
- ZrO 2 was sputtereddeposited onto a clean Silicon wafer by reactive sputtering of a Zirconium target in an Oxygen ambient.
- the film thickness 20 was 135 Angstroms.
- the thickness of the insulator layer typically will be greater than at least 20 Angstroms.
- the PGO thin film 16 was spin coated using lead acetate (Pb(OAc) 2 ⁇ 3H 2 O) and germanium isopropoxide (Ge(OPr′) 4 ) in 2-(2-ethoxyethoxy) ethanol solution (H(OC 2 H 4 OC 2 H 4 OC 2 H 5 ), heated with an air exposure until a deep red brown color.
- the Lead to Germanium ratio (Pb/Ge) was 5.25/3.
- the baking temperature was approximately 50 to 350 degrees Celsius for 30 seconds to 3600 seconds.
- the annealing temperature after each spin-on layer was approximately 400 to 550 degrees Celsius for 30 seconds to 3600 seconds.
- the final annealing temperature was approximately 450 to 600 degrees Celsius for five minutes to three hours.
- the thickness 22 of the PGO layer 16 was approximately 1600 Angstroms and typically will be in a range of 100 Angstroms to 5000 Angstroms.
- the phases of the deposited PGO layer were examined by X-ray diffraction.
- FIG. 2 is a graph of an X-ray diffraction spectrum of a PGO film on a ZrO 2 substrate, as manufactured by the steps listed above.
- the x-axis represents two-times-theta (degrees) and the y-axis represents counts per second.
- the graph shows that substantially pure c-axis PGO was obtained on the ZrO 2 substrate, as shown by the peaks labeled ( 001 ), ( 002 ), ( 003 ), ( 004 ), ( 005 ) and ( 006 ). No other peaks are observed (except for minimal peaks at 29 degrees), which indicates that no reaction, or only a minimal reaction (as shown by the secondary phases at 29 degrees), occurred at the interface of the PGO and ZrO 2 layers.
- FIG. 3 is a graph of a high frequency Capacitance-Voltage (CV) measurement of a metal ferroelectric insulator semiconductor (MFIS) capacitor comprising Pt/PGO/ZrO 2 /Si.
- the x-axis shows voltage and the y-axis shows Capacitance.
- MFIS metal ferroelectric insulator semiconductor
- a Platinum (Pt) top electrode was deposited on the PGO surface with a shallow mask. The area of the top electrode was approximately 4 ⁇ 10 ⁇ 4 cm 2 .
- the PGO film had a thickness of approximately 1600 Angstroms and the ZrO 2 layer had a thickness of approximately 130 Angstroms.
- the hysteresis in the C-V curve indicates a memory window of approximately 0.7 volts.
- the memory window typically will be between 0.1 to 3.0 volts. This is less than the 1.3 volt memory window for an 1800 Angstrom PGO film in a metal ferroelectric metal (MFM) structure.
- MFM metal ferroelectric metal
- FIG. 4 is a graph of a Capacitance-Voltage (CV) measurement of a Pt/PGO(180 nm)/Ir capacitor structure.
- the memory window shown is about 1.8 volts.
- FIG. 5 is a graph of a leakage current (I-V) of a PGO film on a ZrO 2 film. As shown by the graph, the leakage current though the PGO/ZrO 2 structure is very small, indicating that a good interface is maintained between the PGO, the ZrO 2 and the Silicon substrate. In particular, the leakage current typically is less than 1 ⁇ 10 ⁇ 6 A/cm 2 at 100 KV/cm.
- FIG. 6 is a schematic of a preferred embodiment of the composite PGO/insulator layered structure, namely, a metal ferroelectric insulator semiconductor field effect transistor (MFISFET) including a PGO film on an insulator layer.
- Device 30 includes a Semiconductor substrate 32 such as a Silicon substrate, including a source region 34 and a drain region 36 .
- An Insulator film 38 is positioned on substrate 32 .
- Insulator film 38 may comprise Zirconium Oxide (ZrO 2 ), Hafnium Oxide (HfO 2 ), silicates of Zirconium or Hafnium, or mixtures of the above.
- the insulator film 38 may also comprise Aluminum Oxide, Yttrium Oxide, Calcium Oxide, Lanthanum Oxide, Titanium Oxide (TiO 2 ), Tantalum Oxide (Ta 2 O 5 ), doped ZrO 2 or doped HfO 2 , Zr—Al—O, Hf—Al—O, Zr—Ti—O, Hf—Ti—O, and La—Al—O, and combinations thereof.
- the ferroelectric layer 40 comprises a single phase, c-axis Pb 5 Ge 3 O 11 (PGO) film, positioned on insulator film 38 .
- the ferroelectric PGO layer may be deposited by the method set forth in U.S. Pat. Registration No. 6,190,925, issued on Feb.
- a PGO layer can be deposited with a substantially c-axis crystalline orientation, i.e., more than a 70% c-axis orientation, but may be as high as 80%. In a preferred embodiment, the PGO layer will have approximately a 90% c-axis orientation or better.
- a metal top electrode 42 is positioned on PGO film 40 .
- the metal top electrode may comprise Platinum (Pt), Iridium (Ir), Tantalum (Ta), Ruthenium (Ru) or conductive oxides or alloys.
- FIG. 7 is a flowchart of the method of making the PGO-on-insulator structure of the present invention.
- Step 50 comprises preparing the semiconductor substrate using any state of the art process including isolation and well formation.
- Step 52 comprises depositing the insulator film by any of the following means: physical vapor deposition (PVD); evaporation and oxidation; chemical vapor deposition (CVD); and atomic layer deposition.
- Step 54 if required, comprises post deposition annealing of the insulator film in forming gas or Oxygen ambient at a temperature up to 800 degrees Celsius.
- Step 56 comprises depositing the PGO film by any of the following methods: spin-on; physical vapor deposition; CVD; metal organic CVD (MOCVD); chemical solution deposition (CSD); and laser ablation.
- Step 58 comprises depositing the metal gate electrode on the PGO layer by any means known in the art.
- Step 60 comprises making any required contact and interconnect formations.
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Abstract
A thin film structure includes a substantially single-phase, c-axis PGO film on an insulator for use in metal ferroelectric insulator semiconductor single transistor nonvolatile memory applications. The PGO on insulator structure can also be used in capacitors, pyroelectric infrared sensors, optical displays, optical switches, piezoelectric transducers, and surface acoustic wave devices. In a preferred embodiment, the PGO film is deposited on a Zirconium Oxide insulator layer.
Description
- This invention relates to a single c-axis Lead Germanium Oxide (PGO) thin film on an insulator layer for non-volatile memory applications and methods of making the same and, more particularly, to a PGO thin film on a Zirconium Oxide (ZrO2) insulator for ferroelectric random access memory (FeRAM) and dynamic random access memory (DRAM) applications.
- Lead Germanium Oxide (PGO or Pb5Ge3O11) is a well-known ferroelectric material. Pure c-axis oriented PGO thin films have been successfully grown on Iridium (Ir), Platinum (Pt), Platinum/Iridium (Pt/Ir) and Iridium-Tantalum-Oxygen (Ir—Ta—O) conductive electrodes. These structures can be used for metal ferroelectric metal oxide semiconductor (MFMOS) single transistor memory applications.
- Ferroelectric devices have also been manufactured with SrBi2Ta2O9 (SBT). Unlike the ferroelectric material SBT, which exhibits ferroelectric properties with a polycrystalline structure, PGO only exhibits ferroelectric properties when it is c-axis oriented. However, it is rather difficult to grow single-phase c-axis PGO films on insulators because PGO films usually exhibit amorphous or polycrystalline structure.
- Metal ferroelectric semiconductor field effect transistors (MFSFET) are an attractive alternative to MFMOS. However, a strong interaction between the PGO film and the Silicon precludes the fabrication of such devices using a PGO ferroelectric layer. Metal ferroelectric insulator semiconductor field effect transistors (MFISFET) have also been investigated because their structure is simpler than that of MFMOS structures. However, heretofore, good insulator films for fabrication of MFISFET devices, which include a PGO ferroelectric layer, have not been found. Accordingly, there is a need for finding a good insulator film that allows for the fabrication of MFISFET devices having a PGO ferroelectric layer.
- The invention comprises a new thin film structure, including a single-phase c-axis PGO film on an insulator, such as ZrO2, for metal ferroelectric insulator semiconductor single transistor non-volatile memory applications. This PGO-on-insulator structure can also be used in capacitors, pyroelectric infrared sensors, optical displays, optical switches, piezoelectric transducers, and surface acoustic wave devices.
- Accordingly, an object of the invention is to provide a MFIS transistor structure including a PGO ferroelectric film.
- Another object of the invention is to provide a MFIS transistor structure including a ZrO2 insulator film.
- A further object of the invention is to provide a MFIS transistor structure including a PGO ferroelectric layer on an insulator layer.
- FIG. 1 is a schematic of the inventive PGO ferroelectric film on an insulator film.
- FIG. 2 is a graph of an X-ray diffraction spectrum of a PGO film on a ZrO2 insulator film.
- FIG. 3 is a graph of a high frequency Capacitance-Voltage (CV) measurement of a metal ferroelectric insulator semiconductor (MFIS) capacitor comprising Pt/PGO/ZrO2/Si.
- FIG. 4 is a graph of a Capacitance-Voltage (CV) measurement of a Pt/PGO(180 nm)/Ir capacitor structure.
- FIG. 5 is a graph of a leakage current (I-V) of a PGO/ZrO2 film.
- FIG. 6 is a schematic of a metal ferroelectric insulator semiconductor field effect transistor including a PGO layer on an insulator structure.
- FIG. 7 is a flowchart of the method of making the PGO-on-insulator structure of the present invention.
- Turning now to the drawings, FIG. 1 shows a schematic of the inventive device.
Device 10 includes aSemiconductor substrate 12 such as a Silicon substrate. An Insulatorfilm 14, such as ZrO2, is positioned onsubstrate 12. Aferroelectric layer 16, namely, a substantially single phase, c-axis Pb5Ge3O11 (PGO) film, is positioned oninsulator film 14. Ametal top electrode 18 is positioned onPGO film 16. - A typical method for preparing such a structure may include the following steps. First, the semiconductor substrate is prepared using any state of the art process including isolation and well formation. Second, the insulator film, such as ZrO2, is deposited by any of the following means: physical vapor deposition (PVD); evaporation and oxidation; chemical vapor deposition (CVD); and atomic layer deposition. Any necessary post deposition anneal may include annealing in forming gas or Oxygen ambient at a temperature up to 800 degrees Celsius. Third, the PGO film is deposited by any of the following methods: spin-on; physical vapor deposition; CVD; metal organic CVD (MOCVD); chemical solution deposition (CSD); and laser ablation. Fourth, the metal gate electrode is deposited on the PGO layer by any means known in the art. Fifth, the contact and interconnect formations are made.
- As an example, the following device was manufactured. ZrO2 was sputtereddeposited onto a clean Silicon wafer by reactive sputtering of a Zirconium target in an Oxygen ambient. The
film thickness 20, as measured by spectroscopic ellipsometry, was 135 Angstroms. The thickness of the insulator layer typically will be greater than at least 20 Angstroms. The PGOthin film 16 was spin coated using lead acetate (Pb(OAc)2 ·3H2O) and germanium isopropoxide (Ge(OPr′)4) in 2-(2-ethoxyethoxy) ethanol solution (H(OC2H4OC2H4OC2H5), heated with an air exposure until a deep red brown color. The Lead to Germanium ratio (Pb/Ge) was 5.25/3. The baking temperature was approximately 50 to 350 degrees Celsius for 30 seconds to 3600 seconds. The annealing temperature after each spin-on layer was approximately 400 to 550 degrees Celsius for 30 seconds to 3600 seconds. The final annealing temperature was approximately 450 to 600 degrees Celsius for five minutes to three hours. Thethickness 22 of thePGO layer 16 was approximately 1600 Angstroms and typically will be in a range of 100 Angstroms to 5000 Angstroms. The phases of the deposited PGO layer were examined by X-ray diffraction. - FIG. 2 is a graph of an X-ray diffraction spectrum of a PGO film on a ZrO2 substrate, as manufactured by the steps listed above. The x-axis represents two-times-theta (degrees) and the y-axis represents counts per second. The graph shows that substantially pure c-axis PGO was obtained on the ZrO2 substrate, as shown by the peaks labeled (001), (002), (003), (004), (005) and (006). No other peaks are observed (except for minimal peaks at 29 degrees), which indicates that no reaction, or only a minimal reaction (as shown by the secondary phases at 29 degrees), occurred at the interface of the PGO and ZrO2 layers.
- FIG. 3 is a graph of a high frequency Capacitance-Voltage (CV) measurement of a metal ferroelectric insulator semiconductor (MFIS) capacitor comprising Pt/PGO/ZrO2/Si. The x-axis shows voltage and the y-axis shows Capacitance. In order to measure the memory windows of a PGO thin film on a ZrO2 substrate, a Platinum (Pt) top electrode was deposited on the PGO surface with a shallow mask. The area of the top electrode was approximately 4×10−4 cm2. The PGO film had a thickness of approximately 1600 Angstroms and the ZrO2 layer had a thickness of approximately 130 Angstroms. The hysteresis in the C-V curve indicates a memory window of approximately 0.7 volts. The memory window typically will be between 0.1 to 3.0 volts. This is less than the 1.3 volt memory window for an 1800 Angstrom PGO film in a metal ferroelectric metal (MFM) structure.
- FIG. 4 is a graph of a Capacitance-Voltage (CV) measurement of a Pt/PGO(180 nm)/Ir capacitor structure. The memory window shown is about 1.8 volts.
- FIG. 5 is a graph of a leakage current (I-V) of a PGO film on a ZrO2 film. As shown by the graph, the leakage current though the PGO/ZrO2 structure is very small, indicating that a good interface is maintained between the PGO, the ZrO2 and the Silicon substrate. In particular, the leakage current typically is less than 1×10−6 A/cm2 at 100 KV/cm.
- FIG. 6 is a schematic of a preferred embodiment of the composite PGO/insulator layered structure, namely, a metal ferroelectric insulator semiconductor field effect transistor (MFISFET) including a PGO film on an insulator layer.
Device 30 includes aSemiconductor substrate 32 such as a Silicon substrate, including asource region 34 and adrain region 36. AnInsulator film 38 is positioned onsubstrate 32.Insulator film 38 may comprise Zirconium Oxide (ZrO2), Hafnium Oxide (HfO2), silicates of Zirconium or Hafnium, or mixtures of the above. Theinsulator film 38 may also comprise Aluminum Oxide, Yttrium Oxide, Calcium Oxide, Lanthanum Oxide, Titanium Oxide (TiO2), Tantalum Oxide (Ta2O5), doped ZrO2 or doped HfO2, Zr—Al—O, Hf—Al—O, Zr—Ti—O, Hf—Ti—O, and La—Al—O, and combinations thereof. Theferroelectric layer 40 comprises a single phase, c-axis Pb5Ge3O11 (PGO) film, positioned oninsulator film 38. The ferroelectric PGO layer may be deposited by the method set forth in U.S. Pat. Registration No. 6,190,925, issued on Feb. 20, 2001, assigned to Sharp Laboratories of America, Inc., and entitled Epitaxially Grown Lead Germanate Film and Deposition Method, wherein said patent is incorporated herein by reference. By use of the disclosed PGO deposition method as set forth in the above listed patent, a PGO layer can be deposited with a substantially c-axis crystalline orientation, i.e., more than a 70% c-axis orientation, but may be as high as 80%. In a preferred embodiment, the PGO layer will have approximately a 90% c-axis orientation or better. Ametal top electrode 42 is positioned onPGO film 40. The metal top electrode may comprise Platinum (Pt), Iridium (Ir), Tantalum (Ta), Ruthenium (Ru) or conductive oxides or alloys. - FIG. 7 is a flowchart of the method of making the PGO-on-insulator structure of the present invention.
Step 50 comprises preparing the semiconductor substrate using any state of the art process including isolation and well formation.Step 52 comprises depositing the insulator film by any of the following means: physical vapor deposition (PVD); evaporation and oxidation; chemical vapor deposition (CVD); and atomic layer deposition.Step 54, if required, comprises post deposition annealing of the insulator film in forming gas or Oxygen ambient at a temperature up to 800 degrees Celsius. Step 56 comprises depositing the PGO film by any of the following methods: spin-on; physical vapor deposition; CVD; metal organic CVD (MOCVD); chemical solution deposition (CSD); and laser ablation. Step 58 comprises depositing the metal gate electrode on the PGO layer by any means known in the art.Step 60 comprises making any required contact and interconnect formations. - Thus, a single-phase, c-axis PGO thin film on an insulator for non-volatile memory applications, and a method for making the same, has been disclosed. Although preferred structures and methods of manufacturing the device have been disclosed, it should be appreciated that further variations and modifications may be made thereto without departing from the scope of the invention as defined in the appended claims.
Claims (20)
1. A metal ferroelectric insulator semiconductor field effect transistor comprising:
a semiconductor;
a layer of insulator material positioned on said semiconductor; and
a layer of PGO positioned on said layer of insulator material.
2. The transistor of claim 1 wherein said insulator material is chosen from the group consisting of: Zirconium Oxide (ZrO2), Hafnium Oxide (HfO2), silicates of Zirconium, silicates of Hafnium, Aluminum Oxide, Yttrium Oxide, Calcium Oxide, Lanthanum Oxide, Titanium Oxide (TiO2), Tantalum Oxide (Ta2O5), doped ZrO2, doped HfO2, Zr—Al—O, Hf—Al—O, Zr—Ti—O, Hf—Ti—O, La—Al—O, and combinations thereof.
3. The transistor of claim 1 further comprising a top electrode layer positioned on said layer of PGO, wherein said top electrode layer is manufactured of a material chosen from the group consisting of: Platinum (Pt); Iridium (Ir); Tantalum (Ta); Ruthenium (Ru); a conductive oxide; and a conductive alloy.
4. The transistor of claim 1 wherein said layer of PGO comprises a single phase having a c-axis orientation throughout at least 70% of said layer of PGO.
5. The transistor of claim 3 wherein said transistor has a memory window in a range of 0.1 to 3.0 volts.
6. The transistor of claim 3 wherein said semiconductor includes a source region and a drain region.
7. The transistor of claim 1 wherein said layer of PGO has an at least 80% single-phase, c-axis orientation.
8. A thin film semiconductor structure comprising:
a substrate;
a layer of Zirconium Oxide positioned on said substrate; and
a ferroelectric layer of substantially single phase, c-axis oriented PGO positioned on said Zirconium Oxide layer.
9. The structure of claim 8 wherein said semiconductor structure is chosen from the group consisting of: a transistor; a capacitor; a pyroelectric infrared sensor; an optical display; an optical switch; a piezoelectric transducer; and a surface acoustic wave device.
10. The structure of claim 8 wherein said substrate comprises Silicon.
11. The structure of claim 8 wherein said semiconductor structure is a non-volatile memory device.
12. The structure of claim 8 further comprising an electrode positioned on said ferroelectric layer.
13. The structure of claim 8 wherein said ferroelectric layer has a thickness of at least 100 Angstroms.
14. The structure of claim 12 wherein said layer of Zirconium Oxide and said ferroelectric layer define a leakage current, and wherein said leakage current is less than 1×10−6 A/cm2 at 100 KV/cm.
15. A method of making a substantially single phase, c-axis PGO thin film on an insulator for use in a non-volatile memory device, comprising the steps of:
providing a semiconductor substrate;
depositing an insulator film on said semiconductor substrate; and
depositing a PGO film on said insulator film, wherein said PGO film comprises a substantially single phase, c-axis oriented film.
16. The method of claim 15 further comprising depositing a metal gate electrode on said PGO film.
17. The method of claim 15 wherein said semiconductor substrate comprises silicon and said insulator film is chosen from the group consisting of: Zirconium Oxide (ZrO2), Hafnium Oxide (HfO2), silicates of Zirconium, silicates of Hafnium, Aluminum Oxide, Yttrium Oxide, Calcium Oxide, Lanthanum Oxide, Titanium Oxide (TiO2), Tantalum Oxide (Ta2O5), doped ZrO2, doped HfO2, Zr—Al—O, Hf—Al—O, Zr—Ti—O, Hf—Ti—O, La—Al—O, and combinations thereof.
18. The method of claim 15 wherein said step of depositing said insulator film comprises a deposition method chosen from the group consisting of: physical vapor deposition (PVD); evaporation and oxidation; chemical vapor deposition (CVD); and atomic layer deposition.
19. The method of claim 15 wherein said step of depositing said PGO film comprises a deposition method chosen from the group consisting of: spin-on; physical vapor deposition; CVD; metal organic CVD (MOCVD); chemical solution deposition (CSD); and laser ablation.
20. The method of claim 16 wherein said metal gate electrode comprises a material chosen from the group consisting of: Platinum (Pt); Iridium (Ir); Tantalum (Ta); Ruthenium (Ru); a conductive oxide; and a conductive alloy.
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Also Published As
Publication number | Publication date |
---|---|
TW575925B (en) | 2004-02-11 |
US6441417B1 (en) | 2002-08-27 |
JP4020364B2 (en) | 2007-12-12 |
KR20020077203A (en) | 2002-10-11 |
KR100460595B1 (en) | 2004-12-09 |
JP2003023140A (en) | 2003-01-24 |
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