CN104051100B - Titanium oxide multilayer thin film varistor and preparation method for same - Google Patents
Titanium oxide multilayer thin film varistor and preparation method for same Download PDFInfo
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Abstract
The invention relates to a titanium oxide multilayer film varistor and a preparation method for the same, and belongs to the technical field of preparation and application of electronic information materials. Nonstoichiometric sintered TiOm is adopted as a substrate target, other metal or oxide thereof is adopted as a doped substrate, and the thin film varistor employing a TiOy-TiOx-TiOy (y is more than x) sandwich structure as a basic unit is prepared in a radio frequency magnetron sputtering way on a conductive substrate with a smooth surface under the action of carrier gas. The thin film varistor prepared by the method is strict and controllable in deposition condition and high in process repeatability, and a thin film with uniform thickness can be obtained on a large-area substrate. The varistor is high in nonlinear performance and controllable in varistor voltage, is particularly suitable for the over-voltage protection of large-scale or super-large-scale integrated circuits, and has broad application prospect in a power system, a communication system, a security system, motor protection, an automotive electronic system, a household electrical appliance and the like.
Description
Technical field
The present invention relates to a kind of high-performance titanium oxide plural layers piezoresistor and preparation method thereof, belongs to electronic information
Material is prepared and its applied technical field.
Background technology
Piezoresistor (Varistor) to be referred to and have non-linear electricity with a certain particular voltage range at a certain temperature
A kind of semiconductor material devices that stream-voltage characteristic, its resistance are strongly reduced as the voltage for applying increases.Its application is very
Extensively, the over-voltage protection element that can serve as the valve components and various electronic devices and components of suppression transmission line of electricity surge (is called transient state electricity
Stream suppressor or surge suppressor) etc..
At present, business-like piezoresistor is mainly the composite electronic ceramic component with Zinc Oxide as base.It is this
Piezoresistive material is formed with Zinc Oxide and various other additive metal oxide mixed sinterings, wherein constituting varistor
Core material be Zinc Oxide, its structure includes zinc oxide grain and the grain boundary layer around crystal grain, the resistivity of zinc oxide grain
It is very low, and crystal boundary layer resistivity is very high, and Schottky barrier is formed between two for contacting crystal grain, becomes a varistor list
Unit, many units are by being composed in series a piezoresistor.I other words the pressure sensitive quality of zno varistor is from its crystal boundary
Effect.Additionally, having with the composite ceramic voltage dependent resistor device of (such as stannum oxide, titanium oxide etc.) as base other conductor oxidates mostly
There is similar structurally and functionally mechanism.
And developing rapidly with extensive or super large-scale integration, it is desirable to the performance of piezoresistor is higher, device
Part is less, and the low-voltage piezoresistor with ZnO as representative is in computer, communication apparatus, railway signal, motor vehicle assembly, micro electric
Potential in terms of the overvoltage protection of the low-voltage circuit of machine and various other electronic devices receives publicity.As commonly used all kinds of streams at present
The method of prolonging prepares slice type (chip) ZnO base voltage sensitive resistor device.But, the limitation due to sintering ceramic component and the tape casting,
This kind of piezoresistor is difficult to further miniaturization.On the other hand, due to the development of surface engineering technology, filming becomes pressure-sensitive
One effective way of resistor miniaturization, causes extensive concern.Such as Suzuoki etc. utilizes radio frequency sputtering method on a glass substrate
Deposited ZnO/Bi2O3Bilayer film, thickness are respectively 1 μm/0.3 μm, device pressure sensitive voltage ＜ 10V, and with larger non-thread
Property coefficient (Y.Suzuoki, et al.Journal of Physics D：Applied Physics, 1987,20：511-517)；
Horio etc. is prepared for ZnO/Pr using radio frequency sputtering method6O11Bilayer film, thickness are respectively 600nm/400nm, and pressure sensitive voltage is
20V, nonlinear factor be 10 (N.Horio, et al.Vacuum, 1998,51：719-722).Additionally, additive method is used, such as
Sol-gel spray heating decompositions, pulsed laser deposition etc. can also prepare various ZnO polycrystal films piezoresistors.These grind
Study carefully and show, filming is to develop a useful direction of low-voltage piezoresistor, and filming is conducive to miniaturization of components and collection
Cheng Hua.But, there is presently no the report of thin film of titanium oxide piezoresistor.
Additionally, magnetron sputtering method is a kind of ripe film preparing technology, it is widely used；Compared with other methods, magnetic control
Sputtering method deposited thin film material has tack good, and consistency is high, and growth temperature is low, and deposition velocity is fast, can be in different lifes
In long atmosphere the advantages of large-area preparation of thin film material.Therefore, the present invention utilizes radio frequency magnetron sputtering method, with non-stoichiometry
The sintering TiO of ratiomUsed as substrate target, other metals or its oxide are doping target, by controlling magnetron sputtering deposition mistake
The parameters such as sputtering power, atmosphere, base reservoir temperature, sputtering time in journey, design and have prepared one kind first with TiOy-
TiOx-TiOyThin film piezoresitive device of (y ＞ x) sandwich (sandwich) structure for basic structure.This piezoresistor sheet
It is caused by each layer defects concentration is different in its sandwich structure unit in matter.The thin film piezoresitive for preparing in this way
Device, the Nomenclature Composition and Structure of Complexes of material is simple, piezoresistor device shape and film thickness is controllable, compact structure, non-linear behaviour are excellent,
The features such as pressure sensitive voltage is controllable, has wide practical use in the overvoltage protection of extensive or super large-scale integration.And
And preparing proposed thin film piezoresitive in this way, strict controllable, the sputtering technology favorable repeatability of sedimentary condition can be with
The advantages of thin film in uniform thickness is obtained on large area substrates.Technical process is simple and environmentally-friendly, advantageously reduces preparation cost.
The content of the invention
An object of the present invention is to propose a kind of high-performance titanium oxide plural layers piezoresistor, this film type
Piezoresistor group has the controllable the Nomenclature Composition and Structure of Complexes of material simple, piezoresistor device shape and film thickness, compact structure, non-
The features such as linear properties are excellent, pressure sensitive voltage is controllable, is particularly suitable for the overvoltage protection of extensive or super large-scale integration, such as
Have at aspects such as power-supply system, communication system, safety-protection system, motor protection, automobile electronic system, household electrical appliance and widely should
Use prospect.
The second object of the present invention is to provide a kind of system of corresponding high-performance titanium oxide plural layers piezoresistor
Preparation Method.Proposed thin film piezoresitive is prepared in this way, and the strict controllable, sputtering technology of sedimentary condition is repeatable
Well, the advantages of thin film in uniform thickness being obtained on large area substrates.Technical process is simple and environmentally-friendly, advantageously reduces system
Standby cost.
In order to reach above-mentioned target, titanium oxide plural layers piezoresistor proposed by the present invention, it is characterised in that described
Piezoresistor contains one or more TiOy-TiOx-TiOySandwich structure unit.Wherein, levels TiOyLayer and centre
Layer TiOxLayer can be doped using other different metals respectively, it is therefore an objective to realize levels TiO respectivelyyLayer resistivity increases
With intermediate layer TiOxLayer resistivity reduces, so as to improve the non-linear of piezoresistor.
The preparation method of titanium oxide plural layers piezoresistor proposed by the present invention, it is characterised in that methods described is adopted
With the sintering TiO of non-stoichiometricmUsed as substrate target, other metals or its oxide are doping target, by radio-frequency magnetic
Control sputtering, under carrier gas effect, on the bright and clean electricity good conductor substrate of surfacing, prepares with TiOy-TiOx-TiOy
Thin film piezoresitive device of (the y ＞ x) sandwich structure for elementary cell.The method comprising the steps of：
(1) in magnetron sputtering apparatus, with the sintering TiO of non-stoichiometricmAs substrate target, other metals or its
Oxide is doping target, different targets is fixed on different target position, cleaning substrate is fixed on sample stage；Open machinery
Pumping reaches 10 to coarse vacuum, system vacuum-1Molecular pump is opened during Pa, until the vacuum of system reaches 2 × 10-4Pa with
On.
(2) argon working gas are passed through, pre-sputtering are carried out first, the pollutant of target material surface is removed with this；When aura it is steady
After deciding, start thin film sputtering deposition.In depositing inter-layer TiOxDuring thin film, with Ar as sputter gas, in Ar gas atmosphere,
Substrate is room temperature, only sputtering TiOmTarget, control sputtering power and time, sputtering sedimentation obtains TiOxThin film.Depositing upper and lower two-layer
TiOyDuring thin film, with Ar as sputter gas, in Ar, O2In mixed gas, substrate is room temperature, only sputtering TiOmTarget, control sputtering work(
Rate and time, sputtering sedimentation obtain TiOyThin film.In depositing inter-layer doping TiOxDuring thin film, with Ar as sputter gas, in Ar gas
In atmosphere, substrate is room temperature, while sputtering TiOmTarget and doping metals or oxide target, control sputtering power and time, sputtering
Deposition obtains (Ti, M) O of low-resistivityxLaminated film (M is doping metals).Depositing upper and lower two-layer doping TiOyDuring thin film,
With Ar as sputter gas, in Ar, O2In mixed gas, substrate is room temperature, while sputtering TiOmTarget and doping metals or oxide
Target, control sputtering power and time, sputtering sedimentation obtains (Ti, N) O of high resistivityyLaminated film (N is doping metals, but with
M can be different).
(3) the deposition sputter procedure in step (2) is repeated several times, can be obtained containing multiple TiOy-TiOx-TiOyIt is basic to tie
The laminated film piezoresistor of structure unit.
(4) prepared film sample is removed from magnetron sputtering apparatus, obtained final product by electrode respectively on substrate and thin film
To the piezoresistor.
Sintering TiO in above-mentioned preparation method, in the step (1)mIn target, m is between 1.1-1.8.
In above-mentioned preparation method, in the step (2) for the TiO that adulteratesxThe metal of thin film or its oxide target material
For one or more in metal Fe, Co, Ni, Mn and its oxide.
In above-mentioned preparation method, in the step (2) for the TiO that adulteratesyThe metal of thin film or its oxide target material
For metal Bi, Cr, Sb, Ta, Nb and its one kind in oxide.
In above-mentioned preparation method, in the step (1) substrate be highly doped conductive silicon chip, copper sheet, the one kind in platinized platinum.
In above-mentioned preparation method, in the step (2), the purity of argon is in more than 99.99vol.%.
In above-mentioned preparation method, in the step (2), the purity of oxygen is in more than 99.99vol.%.
In above-mentioned preparation method, substrate temperature in the step (2), during deposition, is kept to be room temperature.
In above-mentioned preparation method, the operating air pressure in sputter deposition process in the step (2) is 0.8-2Pa.
In above-mentioned preparation method, the pre-sputtering duration in the step (2) is generally 2-10 minutes.
In above-mentioned preparation method, the sputtering power in the step (2) is 60-140W.
In above-mentioned preparation method, the sputtering sedimentation time of each layer film in the step (2) is identical, respectively 0.5-
2 hours.
In above-mentioned preparation method, upper and lower two-layer TiO of deposition in the step (2)yDuring thin film, Ar/O2Mixed gas volume
Than for 8: 1 to 1: 2.
In above-mentioned preparation method, the upper and lower two-layer doping TiO of deposition in the step (2)yDuring thin film, Ar/O2Mixed gas
Volume ratio is 4: 1 to 1: 4.
In above-mentioned preparation method, the laminated film piezoresistor in the step (3) repeats TiO containing 1-10y-
TiOx-TiOyConstruction unit.
In above-mentioned preparation method, the electrode material in the step (4) be silver, aluminum, palladium, platinum, gold in one kind.
Thin film of titanium oxide is prepared using this technology, with reproducible, sedimentary condition is strictly controllable, can be with extensive deposition
The features such as obtaining uniform thin film, the features such as the piezoresistor for being obtained has pressure-sensitive voltage, high nonlinear coefficient.But,
Because the thickness of thin film is controllable, this piezoresistor either can on high working voltage or low-work voltage electrical equipment
Use.
Description of the drawings
Fig. 1 is proposed by the invention to comprise only a TiOy-TiOx-TiOyThe pressure-sensitive electricity of thin film of titanium oxide of construction unit
Resistance device schematic diagram
Fig. 2 is the current -voltage curve of the thin film of titanium oxide piezoresistor obtained by the embodiment of the present invention 1
Fig. 3 is the current -voltage curve of the thin film of titanium oxide piezoresistor obtained by the embodiment of the present invention 2
Fig. 4 is the current -voltage curve of the thin film of titanium oxide piezoresistor obtained by the embodiment of the present invention 3
Specific embodiment
Technical scheme is described further with reference to embodiment.
The present invention proposes a kind of high performance titanium oxide plural layers piezoresistor, it is characterised in that the pressure-sensitive electricity
Resistance device is with TiOy-TiOx-TiOy(y ＞ x) sandwich structure is elementary cell, wherein levels TiO of each sandwich structurey
Layer and intermediate layer TiOxLayer can be doped using other different metals respectively, realize levels TiO respectivelyyLayer resistivity increases
Big and intermediate layer TiOxThe purpose that layer resistivity reduces, so as to improve the non-linear of piezoresistor.Comprise only a TiOy-
TiOx-TiOyThin film of titanium oxide piezoresistor such as Fig. 1 of construction unit；Laminated film piezoresistor then contains multiple repetitions
TiOy-TiOx-TiOyConstruction unit.
The invention allows for the preparation method of this titanium oxide plural layers piezoresistor, it is characterised in that described
Sintering TiO of the method using non-stoichiometricmUsed as substrate target, other metals or its oxide are doping target, are passed through
The method of rf magnetron sputtering, carrier gas effect under, on the bright and clean electricity good conductor substrate of surfacing, prepare with
TiOy-TiOx-TiOyThin film piezoresitive device of (the y ＞ x) sandwich structure for elementary cell.Methods described passes through radio frequency reaction
Magnetron sputtering deposits the thin film of titanium oxide piezoresistor of different compositions on conductive substrate, comprises the following steps and content：
(1) in magnetron sputtering apparatus, with the sintering TiO of non-stoichiometricm(m=1.1-1.8) as substrate target,
Other metals or its oxide are doping target, different targets are fixed on different target position, cleaning substrate is fixed on sample
On platform；Open mechanical pump and be evacuated to coarse vacuum, system vacuum reaches 10-1Molecular pump is opened during Pa, until the vacuum of system reaches
To 2 × 10-4More than Pa.
(2) working gas high-purity argon gas are passed through, 2-10 minute pre-sputterings are carried out first, the pollution of target material surface is removed with this
Thing；After aura is settled out, in argon or in argon/oxygen mix atmosphere, start sputtering sedimentation TiO successivelyy、TiOxWith
TiOyThin film.
(3) in depositing inter-layer TiOxDuring thin film, with Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-
2Pa, substrate are room temperature, only sputtering TiOmTarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hours, is sputtered
Deposition obtains TiOxThin film.
(4) depositing upper and lower two-layer TiOyDuring thin film, with Ar as sputter gas, in Ar, O2In mixed gas, Ar/O2Mixing
Gas volume ratio is 8: 1 to 1: 2, and operating air pressure is 0.8-2Pa, and substrate is room temperature, only sputtering TiOmTarget, sputtering power are 60-
140W, every layer of sputtering sedimentation are 0.5-2 hours, and sputtering sedimentation obtains TiOyThin film
(5) in depositing inter-layer doping TiOxDuring thin film, with Ar as sputter gas, in Ar gas atmosphere, operating air pressure is
0.8-2Pa, substrate are room temperature, while sputtering TiOmTarget and doping metals or oxide target, sputtering power is 60-140W, per layer
Sputtering sedimentation is 0.5-2 hours, and sputtering sedimentation obtains (Ti, M) O of low-resistivityxLaminated film (M is doping metals).
(6) depositing upper and lower two-layer doping TiOyDuring thin film, with Ar as sputter gas, in Ar, O2In mixed gas, Ar/O2
Mixed gas volume ratio is 4: 1 to 1: 4, and operating air pressure is 0.8-2Pa, and substrate is room temperature, while sputtering TiOmTarget and doping gold
Category or oxide target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hours, and sputtering sedimentation obtains high resistivity
(Ti, N) OyLaminated film (N is doping metals, but can be different from M).
(7) if necessary to plural layers varistor, the deposition sputter procedure in step (2) to (6) is repeated, is contained
Multiple TiOy-TiOx-TiOyThe laminated film piezoresistor of basic structural unit.
(8) prepared film sample is removed from magnetron sputtering apparatus, obtained final product by electrode respectively on substrate and thin film
To the piezoresistor.
(9) the used working gas of whole experiment is high-purity gas, more than purity 99.99vol.%.
(10) substrate be highly doped conductive silicon chip, copper sheet, the one kind in platinized platinum.
(11) electrode material be silver, aluminum, palladium, platinum, gold in one kind.
(12) the doping target material, for the TiO that adulteratesxThin film in metal Fe, Co, Ni, Mn and its oxide
One or more；For the TiO that adulteratesyThin film for metal Bi, Cr, Sb, Ta, Nb and its one kind in oxide.
Resulting thin film piezoresitive device is white film in appearance.
Under a scanning electron microscope, it may be observed that the surface compact pore-free of thin film.Current-voltage performance test table
Bright, the thin film of this structure has good pressure-sensitive character.
In a word, high performance titanium oxide piezoresistor can be obtained with this technology.
Embodiment 1：By TiO1.3Target and the highly doped conductive silicon chip of cleaning are fixed on the relevant position of magnetron sputtering apparatus
On, chamber is closed, mechanical pump is first opened and is evacuated to coarse vacuum 10-1Pa, is then turned on molecular pump and is evacuated to fine vacuum 2 × 10-4Pa.It is passed through
High-purity argon gas, pre-sputtering 10 minutes.Then pass to Ar/O2Than the mixed gas for 4: 1, under conditions of sputtering power is 60W, sink
Product 1 hour.Oxygen valve is closed, only logical argon, under conditions of sputtering power is 60W, deposited 1 hour.Ar/O is passed through again2Than for
4: 1 mixed gas, under conditions of sputtering power is 60W, deposit 1 hour.Can obtain containing a TiO on substratey-
TiOx-TiOyThe undoped plural layers of construction unit.Overall process is carried out at room temperature, operating air pressure 0.8-2Pa.In sample table
Face applies silver as electrode, and lead of burn-oning obtains piezoresistor, tests its voltage-dependent characteristic.The TiO for being obtainedy-TiOx-TiOy
Plural layers piezoresistor structure is fine and close, surface pore-free, and pressure sensitive voltage is 115627V/mm, nonlinear factor be 11 (see
Fig. 2).
Embodiment 2：By TiO1.3Target and the highly doped conductive silicon chip of cleaning are fixed on the relevant position of magnetron sputtering apparatus
On, chamber is closed, mechanical pump is first opened and is evacuated to coarse vacuum 10-1Pa, is then turned on molecular pump and is evacuated to fine vacuum 2 × 10-4Pa.It is passed through
High-purity argon gas, pre-sputtering 10 minutes.Then pass to Ar/O2Than the mixed gas for 4: 1, under conditions of sputtering power is 60W, sink
Product 1 hour.Oxygen valve is closed, only logical argon, under conditions of sputtering power is 60W, deposited 1 hour.Ar/O is passed through again2Than for
4: 1 mixed gas, under conditions of sputtering power is 60W, deposit 1 hour.Oxygen valve is again switched off, only logical argon, sputters work(
Under conditions of rate is 60W, deposit 1 hour.Then Ar/O is passed through again2Than the mixed gas for 4: 1, bar of the sputtering power for 60W
Under part, deposit 1 hour.Can obtain containing two TiO on substratey-TiOx-TiOyThe undoped plural layers of construction unit.
Overall process is carried out at room temperature, operating air pressure 0.8-2Pa.Silver is applied as electrode in sample surfaces, lead of burn-oning obtains pressure-sensitive
Resistor, tests its voltage-dependent characteristic.The TiO for being obtainedy-TiOx-TiOyPlural layers piezoresistor structure is fine and close, surface without
Pore, pressure sensitive voltage are 97325V/mm, and nonlinear factor is 16 (see Fig. 3).
Embodiment 3：By TiO1.8Target, pure Fe targets and the highly doped conductive silicon chip of cleaning are fixed on magnetron sputtering apparatus
On relevant position, chamber is closed, first open mechanical pump and be evacuated to coarse vacuum 10-1Pa, is then turned on molecular pump and is evacuated to fine vacuum 2 × 10- 4Pa.It is passed through high-purity argon gas, pre-sputtering 2 minutes.Then pass to Ar/O2Than the mixed gas for 1: 2, bar of the sputtering power for 60W
Under part, deposit 1 hour.Oxygen valve is closed, only logical argon, while opening TiO1.8Target and pure Fe targets, sputtering power are 60W
Under conditions of, deposit 1 hour.Ar/O is passed through again2Than the mixed gas for 1: 2, under conditions of sputtering power is 60W, deposition 1
Hour.Can obtain on substrate that intermediate layer mixes ferrum contains TiOy-TiOx-TiOyThe plural layers of construction unit.Overall process exists
Carry out under room temperature, operating air pressure 0.8-2Pa.Silver is applied as electrode in sample surfaces, lead of burn-oning obtains piezoresistor,
Test its voltage-dependent characteristic.The TiO for being obtainedy- (Ti, Fe) Ox-TiOyPlural layers piezoresistor structure is fine and close, surface depletion of QI
Hole, pressure sensitive voltage are 75084V/mm, and nonlinear factor is 21 (see Fig. 4).
Claims (3)
1. a kind of titanium oxide plural layers piezoresistor, it is characterised in that the piezoresistor contains one or more
TiOy-TiOx-TiOySandwich structure unit；Sandwich structure levels TiOyLayer is undoped titanium oxide or is gold
A kind of titanium oxide of the doping in category Bi, Cr, Sb, Ta, Nb and its oxide, the sandwich structure intermediate layer TiOxLayer is non-
Adulterated TiOx or the titanium oxide for one or more doping in metal Fe, Co, Ni, Mn and its oxide, and y is more than x.
2. according to the preparation method of the titanium oxide plural layers piezoresistor described in claim 1, it is characterised in that the side
Sintering TiO of the method using non-stoichiometricmUsed as substrate target, metal Bi, Cr, Sb, Ta, Nb or its oxide are levels
TiOyThe doping target of layer, metal Fe, Co, Ni, Mn or its oxide are intermediate layer TiOxThe doping target of layer, by radio-frequency magnetic
Control sputtering, under carrier gas effect, on the bright and clean electricity good conductor substrate of surfacing, prepares the TiO of the x of ＞ containing yy-
TiOx-TiOyThin film piezoresitive device of the sandwich structure for elementary cell；
The preparation method is comprised the following steps：(1) in magnetron sputtering apparatus, by TiOmSubstrate target and doping target difference
It is fixed on different target position, cleaning substrate is fixed on sample stage；Open mechanical pump and be evacuated to coarse vacuum, system vacuum reaches
10-1Molecular pump is opened during Pa, until the vacuum of system reaches 2 × 10-4More than Pa；(2) argon is passed through, pre- splashing is carried out first
2-10 minutes are penetrated, to remove the pollutant of target material surface；After aura is settled out, in argon or in argon/oxygen mixture
In atmosphere, start sputtering sedimentation TiO successivelyy、TiOxAnd TiOyThin film；(3) the deposition sputter procedure in step (2) is repeated several times, can
To obtain containing multiple TiOy-TiOx-TiOyThe complex multi layer films piezoresistor of basic structural unit；(4) set from magnetron sputtering
Standby film sample prepared by middle removal, is obtained the piezoresistor by electrode respectively on substrate and thin film.
3. according to the preparation method described in claim 2, it is characterised in that the TiOmIn substrate target, m is between 1.1-1.8；
The substrate is highly doped conductive silicon chip, copper sheet, the one kind in platinized platinum；The argon and oxygen are high-purity gas, and purity exists
In more than 99.99vol.%；The electrode material be silver, aluminum, palladium, platinum, gold in one kind；The doping target material, for mixing
Miscellaneous TiOxThin film for one or more in metal Fe, Co, Ni, Mn and its oxide；For the TiO that adulteratesyThin film for metal
One kind in Bi, Cr, Sb, Ta, Nb and its oxide；In depositing inter-layer TiOxDuring thin film, with Ar as sputter gas, in Ar gas
In atmosphere, operating air pressure is 0.8-2Pa, and substrate is room temperature, only sputtering TiOmTarget, sputtering power is 60-140W, and per layer of sputtering is heavy
Product is 0.5-2 hours, and sputtering sedimentation obtains TiOxThin film；Depositing upper and lower two-layer TiOyDuring thin film, with Ar as sputter gas,
In Ar, O2In mixed gas, Ar/O2Mixed gas volume ratio is 8: 1 to 1: 2, and operating air pressure is 0.8-2Pa, and substrate is room temperature,
TiO is sputtered onlymTarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hours, and sputtering sedimentation obtains TiOyThin film；
In depositing inter-layer doping TiOxDuring thin film, with Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-2Pa, substrate
For room temperature, while sputtering TiOmTarget and metal Fe, Co, Ni, Mn and its one or more doping metals in oxide or oxidation
Thing target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hours, and sputtering sedimentation obtains the metal M of low-resistivity
Adulterated TiOx (Ti, M) OxLaminated film；Depositing upper and lower two-layer doping TiOyDuring thin film, with Ar as sputter gas, in Ar, O2
In mixed gas, Ar/O2Mixed gas volume ratio is 4: 1 to 1: 4, and operating air pressure is 0.8-2Pa, and substrate is room temperature, while splashing
Penetrate TiOmTarget and metal Bi, Cr, Sb, Ta, Nb and its a kind of doping metals or oxide target in oxide, sputtering power is
60-140W, every layer of sputtering sedimentation are 0.5-2 hours, and sputtering sedimentation obtains metal N adulterated TiOxes (Ti, N) of high resistivity
OyLaminated film.
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| CN104649661B (en) * | 2014-12-10 | 2016-12-07 | 昆明理工大学 | A kind of codope TiO2the method of voltage-sensitive ceramic, codope TiO2varistor and preparation method thereof |
| CN105869807B (en) * | 2016-05-03 | 2017-11-24 | 中国地质大学（北京） | A kind of preparation method of zinc oxide bismuth thin film piezoresistor |
| CN108218420B (en) * | 2017-05-25 | 2020-11-20 | 湖北文理学院 | Titanium dioxide high-voltage piezoresistor and preparation method thereof |
| CN109536904B (en) * | 2018-12-10 | 2021-05-14 | 河南科技大学 | Doped TiO (titanium dioxide)2Barrier layer film and preparation method thereof |
| CN114807877B (en) * | 2021-01-19 | 2023-11-10 | 中国科学院上海硅酸盐研究所 | Black titanium dioxide photocatalytic film and preparation method and application thereof |
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| US4272754A (en) * | 1979-12-17 | 1981-06-09 | General Electric Company | Thin film varistor |
| EP1480233A1 (en) * | 2002-02-28 | 2004-11-24 | Kojima Chemicals Co., Ltd | Resistor |
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| CN102643086A (en) * | 2012-02-22 | 2012-08-22 | 中国地质大学（北京） | Stannic oxide based piezoresistor material and preparation method thereof |
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| Characterizations of phosphorus doped ZnO;Sung Hoon Lim et al;《superlattices and microstructures》;20050919;第38卷;第377-384 * |
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