CN104051100A - Titanium oxide multilayer thin film varistor and preparation method for same - Google Patents
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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 varistor and preparation method thereof, belong to electronic information material preparation and applied technical field thereof.
Background technology
Varistor (Varistor) refer at a certain temperature with a certain particular voltage range in there is nonlinear current-voltage, its resistance along with the voltage applying increases and a kind of semi-conducting material device of sharply reducing.Its application is very wide, can be as suppressing the valve element of transmission line surge and the over-voltage protection element (being again transient current inhibitor or surge suppressor) of various electronic devices and components etc.
At present, business-like varistor is mainly to take the composite material electronic ceramic element that zinc oxide is base.This piezoresistive material is to form with zinc oxide and multiple other additive metal oxide mixed sinterings, the core material that wherein forms piezo-resistance is zinc oxide, its structure comprises zinc oxide grain and crystal grain grain boundary layer around, the resistivity of zinc oxide grain is very low, and grain boundary layer resistivity is very high, two intergranules that contact form Schottky barrier, become a piezo-resistance unit, and many unit are by being composed in series a varistor.That is to say that the pressure sensitive quality of zno varistor is from its grain boundary effect.In addition, take the composite ceramic voltage dependent resistor device that other conductor oxidates (as tin oxide, titanium oxide etc.) are base has similar structure and mechanism of action mostly.
And along with the develop rapidly of extensive or very lagre scale integrated circuit (VLSIC); require the performance of varistor higher; device is less, and the low-voltage piezoresistor that the ZnO of take is representative receives publicity at the potential aspect the overvoltage protection of the low-voltage circuit of computer, communication apparatus, railway signal, motor vehicle assembly, micromachine and various other electronic devices.As at present conventional all kinds of the tape casting are prepared slice type (chip) ZnO base voltage sensitive resistor device.But due to the limitation of sintered ceramic device and the tape casting, this class varistor is difficult to further miniaturization.On the other hand, due to the development of surface engineering technology, filming becomes an effective way of varistor miniaturization, causes extensive concern.As Suzuoki etc. utilizes radio frequency sputtering method to deposit ZnO/Bi on glass substrate
2o
3bilayer film, thickness is respectively 1 μ m/0.3 μ m, device pressure sensitive voltage < 10V, and there is larger non linear coefficient (Y.Suzuoki, et al.Journal of Physics D:Applied Physics, 1987,20:511-517); Horio etc. utilize radio frequency sputtering method to prepare ZnO/Pr
6o
11bilayer film, thickness is respectively 600nm/400nm, pressure sensitive voltage is 20V, non linear coefficient be 10 (N.Horio, et al.Vacuum, 1998,51:719-722).In addition, use additive method, as sol-gel spray heating decomposition, pulsed laser deposition etc. also can be prepared various ZnO polycrystal film varistors.These researchs show, filming is a useful direction of exploitation low-voltage piezoresistor, and filming is conducive to miniaturization of components and integrated.But, the current report that also there is no thin film of titanium oxide varistor.
In addition, magnetron sputtering method is a kind of film preparing technology of maturation, is widely used; Compare with other method, it is good that magnetron sputtering method deposit film material has tack, and density is high, and growth temperature is low, and deposition velocity is fast, can be in different growth atmospheres the advantage such as large-area preparation of thin film material.Therefore, the present invention utilizes radio frequency magnetron sputtering method, with the sintering TiO of non-stoichiometric
mas matrix target, other metals or its oxide are doping target, by parameters such as the sputtering power in control magnetron sputtering deposition process, atmosphere, base reservoir temperature, sputtering times, design first and prepared a kind of with TiO
y-TiO
x-TiO
ythe thin film sensitive resistor that (y > x) sandwich (sandwich) structure is basic structure.This varistor is that in its sandwich structure unit, each layer defects concentration difference causes in essence.The thin film sensitive resistor of preparing in this way; the features such as the Nomenclature Composition and Structure of Complexes of material is simple, varistor device shape and film thickness is controlled, compact structure, non-linear behaviour is excellent, pressure sensitive voltage is controlled have wide practical use in the overvoltage protection of extensive or very lagre scale integrated circuit (VLSIC).And the film piezo-resistance that preparation proposes in this way, sedimentary condition is controlled, sputtering technology favorable repeatability strictly, can on large area substrates, obtain the advantages such as film of even thickness.Technical process is simple, environmental protection, is conducive to reduce preparation cost.
Summary of the invention
One of object of the present invention is to propose a kind of high-performance titanium oxide plural layers varistor; the features such as the Nomenclature Composition and Structure of Complexes that this film-type varistor group has material is simple, varistor device shape and film thickness is controlled, compact structure, non-linear behaviour is excellent, pressure sensitive voltage is controlled; be particularly suitable for the overvoltage protection of extensive or very lagre scale integrated circuit (VLSIC), as having wide practical use at aspects such as power-supply system, communication system, safety-protection system, motor protection, automobile electronic system, household electrical appliance.
Two of object of the present invention is to provide a kind of preparation method of corresponding high-performance titanium oxide plural layers varistor.The film piezo-resistance that preparation proposes in this way, sedimentary condition is controlled, sputtering technology favorable repeatability strictly, can on large area substrates, obtain the advantages such as film of even thickness.Technical process is simple, environmental protection, is conducive to reduce preparation cost.
In order to reach above-mentioned target, the titanium oxide plural layers varistor that the present invention proposes, is characterized in that, described varistor contains one or more TiO
y-TiO
x-TiO
ysandwich structure unit.Wherein, levels TiO
ylayer and intermediate layer TiO
xlayer can be used respectively other different metals to adulterate, and object is to realize respectively levels TiO
ylayer resistivity increases and intermediate layer TiO
xlayer resistivity reduces, thereby improves the non-linear of varistor.
The preparation method of the titanium oxide plural layers varistor that the present invention proposes, is characterized in that, described method adopts the sintering TiO of non-stoichiometric
mas matrix target, other metals or its oxide, for doping target, by rf magnetron sputtering, under carrier gas effect, on the bright and clean electricity good conductor substrate of surfacing, prepare with TiO
y-TiO
x-TiO
ythe thin film sensitive resistor that (y > x) sandwich structure is elementary cell.Said method comprising the steps of:
(1) in magnetron sputtering apparatus, with the sintering TiO of non-stoichiometric
mas matrix target, other metals or its oxide, for doping target, are fixed on different targets on different target position, and cleaning substrate is fixed on sample stage; Open mechanical pump and be evacuated to low vacuum, system vacuum degree reaches 10
-1during Pa, open molecular pump, until the vacuum degree of system reaches 2 * 10
-4more than Pa.
(2) pass into working gas argon gas, first carry out pre-sputtering, with this, remove the pollutant of target material surface; After aura settles out, start thin film sputtering deposition.At deposition intermediate layer TiO
xduring film, take Ar as sputter gas, in Ar gas atmosphere, substrate is room temperature, a sputtered with Ti O
mtarget, controls sputtering power and time, and sputtering sedimentation obtains TiO
xfilm.At the upper and lower two-layer TiO of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, substrate is room temperature, a sputtered with Ti O
mtarget, controls sputtering power and time, and sputtering sedimentation obtains TiO
yfilm.At deposition intermediate layer doped Ti O
xduring film, take Ar as sputter gas, in Ar gas atmosphere, substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, control sputtering power and time, and sputtering sedimentation obtains (Ti, M) O of low-resistivity
xlaminated film (M is doping metals).At the upper and lower two-layer doped Ti O of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, control sputtering power and time, and sputtering sedimentation obtains (Ti, N) O of high resistivity
ylaminated film (N is doping metals, but from M can be different).
(3) the deposition sputter procedure in repeating step (2) repeatedly, can obtain containing a plurality of TiO
y-TiO
x-TiO
ythe laminated film varistor of basic structural unit.
(4) from magnetron sputtering apparatus, shift out prepared film sample, respectively on substrate and film by electrode, obtain described varistor.
In above-mentioned preparation method, the sintering TiO in described step (1)
min target, m is between 1.1-1.8.
In above-mentioned preparation method, in described step (2) for doped Ti O
xthe metal of film or its oxide target material are one or more in metal Fe, Co, Ni, Mn and oxide thereof.
In above-mentioned preparation method, in described step (2) for doped Ti O
ythe metal of film or its oxide target material are a kind of in metal Bi, Cr, Sb, Ta, Nb and oxide thereof.
In above-mentioned preparation method, substrate is a kind of in highly doped conductive silicon chip, copper sheet, platinized platinum in described step (1).
In above-mentioned preparation method, in described step (2), the purity of argon gas is more than 99.99vol.%.
In above-mentioned preparation method, in described step (2), the purity of oxygen is more than 99.99vol.%.
In above-mentioned preparation method, while depositing in described step (2), keeping substrate temperature is room temperature.
In above-mentioned preparation method, the operating air pressure in the sputter deposition process in described step (2) is 0.8-2Pa.
In above-mentioned preparation method, the pre-sputtering duration in described step (2) is generally 2-10 minute.
In above-mentioned preparation method, the sputtering power in described step (2) is 60-140W.
In above-mentioned preparation method, the sputtering sedimentation time of each layer film in described step (2) is identical, is respectively 0.5-2 hour.
In above-mentioned preparation method, the upper and lower two-layer TiO of deposition in described step (2)
yduring film, Ar/O
2mist volume ratio is 8: 1 to 1: 2.
In above-mentioned preparation method, the upper and lower two-layer doped Ti O of deposition in described step (2)
yduring film, Ar/O
2mist volume ratio is 4: 1 to 1: 4.
In above-mentioned preparation method, the laminated film varistor in described step (3) repeats TiO containing 1-10
y-TiO
x-TiO
yconstruction unit.
In above-mentioned preparation method, the electrode material in described step (4) is a kind of in silver, aluminium, palladium, platinum, gold.
Adopt this technology to prepare thin film of titanium oxide, have reproduciblely, sedimentary condition is strictly controlled, can large area deposition obtain the features such as homogeneous film, and the varistor obtaining has the features such as pressure-sensitive voltage, high nonlinear coefficient.But because the thickness of film is controlled, no matter this varistor is can use on high working voltage or low-work voltage electrical equipment.
Accompanying drawing explanation
Fig. 1 is the proposed by the invention TiO that only contains
y-TiO
x-TiO
ythe thin film of titanium oxide varistor schematic diagram of construction unit
Fig. 2 is the current-voltage curve of the prepared thin film of titanium oxide varistor of the embodiment of the present invention 1
Fig. 3 is the current-voltage curve of the prepared thin film of titanium oxide varistor of the embodiment of the present invention 2
Fig. 4 is the current-voltage curve of the prepared thin film of titanium oxide varistor of the embodiment of the present invention 3
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
The present invention proposes a kind of high performance titanium oxide plural layers varistor, it is characterized in that, described varistor is with TiO
y-TiO
x-TiO
y(y > x) sandwich structure is elementary cell, wherein the levels TiO of each sandwich structure
ylayer and intermediate layer TiO
xlayer can be used respectively other different metals to adulterate, and realizes respectively levels TiO
ylayer resistivity increases and intermediate layer TiO
xthe object that layer resistivity reduces, thus the non-linear of varistor improved.Only contain a TiO
y-TiO
x-TiO
ythe thin film of titanium oxide varistor of construction unit is as Fig. 1; Laminated film varistor contains the TiO of a plurality of repetitions
y-TiO
x-TiO
yconstruction unit.
The preparation method who the invention allows for this titanium oxide plural layers varistor, is characterized in that, described method adopts the sintering TiO of non-stoichiometric
mas matrix target, other metals or its oxide, for doping target, by the method for rf magnetron sputtering, under carrier gas effect, on the bright and clean electricity good conductor substrate of surfacing, prepare with TiO
y-TiO
x-TiO
ythe thin film sensitive resistor that (y > x) sandwich structure is elementary cell.Described method deposits the different thin film of titanium oxide varistors that form by radio frequency reaction magnetron sputtering on conductive substrate, comprises the following steps and content:
(1) in magnetron sputtering apparatus, with the sintering TiO of non-stoichiometric
m(m=1.1-1.8), as matrix target, other metals or its oxide, for doping target, are fixed on different targets on different target position, and cleaning substrate is fixed on sample stage; Open mechanical pump and be evacuated to low vacuum, system vacuum degree reaches 10
-1during Pa, open molecular pump, until the vacuum degree of system reaches 2 * 10
-4more than Pa.
(2) pass into working gas high-purity argon gas, first carry out 2-10 minute pre-sputtering, with this, remove the pollutant of target material surface; After aura settles out, at argon gas or in argon gas/oxygen mix atmosphere, start sputtering sedimentation TiO successively
y, TiO
xand TiO
yfilm.
(3) at deposition intermediate layer TiO
xduring film, take Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-2Pa, and substrate is room temperature, a sputtered with Ti O
mtarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains TiO
xfilm.
(4) at the upper and lower two-layer TiO of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, Ar/O
2mist volume ratio is 8: 1 to 1: 2, and operating air pressure is 0.8-2Pa, and substrate is room temperature, a sputtered with Ti O
mtarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains TiO
yfilm
(5) at deposition intermediate layer doped Ti O
xduring film, take Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-2Pa, and substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains (Ti, M) O of low-resistivity
xlaminated film (M is doping metals).
(6) at the upper and lower two-layer doped Ti O of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, Ar/O
2mist volume ratio is 4: 1 to 1: 4, and operating air pressure is 0.8-2Pa, and substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains (Ti, N) O of high resistivity
ylaminated film (N is doping metals, but from M can be different).
(7), if need plural layers piezo-resistance, the deposition sputter procedure in can repeating step (2) to (6), obtains containing a plurality of TiO
y-TiO
x-TiO
ythe laminated film varistor of basic structural unit.
(8) from magnetron sputtering apparatus, shift out prepared film sample, respectively on substrate and film by electrode, obtain described varistor.
(9) working gas that whole experiment is used is high-purity gas, more than purity 99.99vol.%.
(10) described substrate is a kind of in highly doped conductive silicon chip, copper sheet, platinized platinum.
(11) described electrode material is a kind of in silver, aluminium, palladium, platinum, gold.
(12) described doping target material, for doped Ti O
xfilm be one or more in metal Fe, Co, Ni, Mn and oxide thereof; For doped Ti O
yfilm be a kind of in metal Bi, Cr, Sb, Ta, Nb and oxide thereof.
Resulting thin film sensitive resistor is white film in appearance.
Under scanning electron microscopy, can observe the surface compact pore-free of film.Current-voltage performance test shows, the film of this structure has good pressure-sensitive character.
In a word, by this technology, can obtain high performance titanium oxide varistor.
Embodiment 1: by TiO
1.3target and clean highly doped conductive silicon substrate are fixed on the relevant position of magnetron sputtering apparatus, close chamber, first open mechanical pump and are evacuated to low vacuum 10
-1pa, then open molecular pump and be evacuated to high vacuum 2 * 10
-4pa.Pass into high-purity argon gas, pre-sputtering 10 minutes.Then pass into Ar/O
2than the mist that is 4: 1, under the condition that sputtering power is 60W, deposit 1 hour.Close oxygen valve, only logical argon gas, under the condition that sputtering power is 60W, deposits 1 hour.Again pass into Ar/O
2than the mist that is 4: 1, under the condition that sputtering power is 60W, deposit 1 hour.Can on substrate, obtain and contain a TiO
y-TiO
x-TiO
ythe non-doped multi-layer film of construction unit.Overall process is at room temperature carried out, operating air pressure 0.8-2Pa.At sample surfaces, be coated with silver as electrode, the lead-in wire of burn-oning, obtains varistor, tests its voltage-dependent characteristic.The TiO obtaining
y-TiO
x-TiO
yplural layers piezoresistor structure is fine and close, surperficial pore-free, and pressure sensitive voltage is 115627V/mm, non linear coefficient is 11 (seeing Fig. 2).
Embodiment 2: by TiO
1.3target and clean highly doped conductive silicon substrate are fixed on the relevant position of magnetron sputtering apparatus, close chamber, first open mechanical pump and are evacuated to low vacuum 10
-1pa, then open molecular pump and be evacuated to high vacuum 2 * 10
-4pa.Pass into high-purity argon gas, pre-sputtering 10 minutes.Then pass into Ar/O
2than the mist that is 4: 1, under the condition that sputtering power is 60W, deposit 1 hour.Close oxygen valve, only logical argon gas, under the condition that sputtering power is 60W, deposits 1 hour.Again pass into Ar/O
2than the mist that is 4: 1, under the condition that sputtering power is 60W, deposit 1 hour.Again close oxygen valve, only logical argon gas, under the condition that sputtering power is 60W, deposits 1 hour.And then pass into Ar/O
2than the mist that is 4: 1, under the condition that sputtering power is 60W, deposit 1 hour.Can on substrate, obtain and contain two TiO
y-TiO
x-TiO
ythe non-doped multi-layer film of construction unit.Overall process is at room temperature carried out, operating air pressure 0.8-2Pa.At sample surfaces, be coated with silver as electrode, the lead-in wire of burn-oning, obtains varistor, tests its voltage-dependent characteristic.The TiO obtaining
y-TiO
x-TiO
yplural layers piezoresistor structure is fine and close, surperficial pore-free, and pressure sensitive voltage is 97325V/mm, non linear coefficient is 16 (seeing Fig. 3).
Embodiment 3: by TiO
1.8target, pure Fe target and clean highly doped conductive silicon substrate are fixed on the relevant position of magnetron sputtering apparatus, close chamber, first open mechanical pump and are evacuated to low vacuum 10
-1pa, then open molecular pump and be evacuated to high vacuum 2 * 10
-4pa.Pass into high-purity argon gas, pre-sputtering 2 minutes.Then pass into Ar/O
2than the mist that is 1: 2, under the condition that sputtering power is 60W, deposit 1 hour.Close oxygen valve, only logical argon gas is opened TiO simultaneously
1.8target and pure Fe target, sputtering power is under the condition of 60W, deposits 1 hour.Again pass into Ar/O
2than the mist that is 1: 2, under the condition that sputtering power is 60W, deposit 1 hour.Can on substrate, obtain intermediate layer and mix the TiO that contains of iron
y-TiO
x-TiO
ythe plural layers of construction unit.Overall process is at room temperature carried out, operating air pressure 0.8-2Pa.At sample surfaces, be coated with silver as electrode, the lead-in wire of burn-oning, obtains varistor, tests its voltage-dependent characteristic.The TiO obtaining
y-(Ti, Fe) O
x-TiO
yplural layers piezoresistor structure is fine and close, surperficial pore-free, and pressure sensitive voltage is 75084V/mm, non linear coefficient is 21 (seeing Fig. 4).
Claims (3)
1. a titanium oxide plural layers varistor, is characterized in that, described varistor contains one or more TiO
y-TiO
x-TiO
ysandwich structure unit; Described sandwich structure levels TiO
ylayer is non-adulterated TiOx or is other metals or its oxide-doped titanium oxide, described sandwich structure intermediate layer TiO
xlayer is non-adulterated TiOx or is other metals or oxide-doped titanium oxide, and y is greater than x.
2. according to the preparation method of titanium oxide plural layers varistor claimed in claim 1, it is characterized in that, described method adopts the sintering TiO of non-stoichiometric
mas matrix target, other metals or its oxide, for doping target, by rf magnetron sputtering, under carrier gas effect, on the bright and clean electricity good conductor substrate of surfacing, prepare with TiO
y-TiO
x-TiO
ythe thin film sensitive resistor that (y > x) sandwich structure is elementary cell;
Described preparation method comprises the following steps: (1) is in magnetron sputtering apparatus, by TiO
mmatrix target and doping target are separately fixed on different target position, and cleaning substrate is fixed on sample stage; Open mechanical pump and be evacuated to low vacuum, system vacuum degree reaches 10
-1during Pa, open molecular pump, until the vacuum degree of system reaches 2 * 10
-4more than Pa; (2) pass into argon gas, first carry out pre-sputtering 2-10 minute, to remove the pollutant of target material surface; After aura settles out, at argon gas or in argon gas/oxygen mix atmosphere, start sputtering sedimentation TiO successively
y, TiO
xand TiO
yfilm; (3) the deposition sputter procedure in repeating step (2) repeatedly, can obtain containing a plurality of TiO
y-TiO
x-TiO
ythe composite multi-layer thin film sensitive resistor of basic structural unit; (4) from magnetron sputtering apparatus, shift out prepared film sample, respectively on substrate and film by electrode, obtain described varistor.
3. according to preparation method claimed in claim 2, it is characterized in that (1) described TiO
min matrix target, m is between 1.1-1.8; (2) described substrate is a kind of in highly doped conductive silicon chip, copper sheet, platinized platinum; (3) described argon gas and oxygen are high-purity gas, and purity is more than 99.99vol.%; (4) described electrode material is a kind of in silver, aluminium, palladium, platinum, gold; (5) described doping target material, for doped Ti O
xfilm be one or more in metal Fe, Co, Ni, Mn and oxide thereof; For doped Ti O
yfilm be a kind of in metal Bi, Cr, Sb, Ta, Nb and oxide thereof; (6) at deposition intermediate layer TiO
xduring film, take Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-2Pa, and substrate is room temperature, a sputtered with Ti O
mtarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains TiO
xfilm; At the upper and lower two-layer TiO of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, Ar/O
2mist volume ratio is 8: 1 to 1: 2, and operating air pressure is 0.8-2Pa, and substrate is room temperature, a sputtered with Ti O
mtarget, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains TiO
yfilm; At deposition intermediate layer doped Ti O
xduring film, take Ar as sputter gas, in Ar gas atmosphere, operating air pressure is 0.8-2Pa, and substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains (Ti, M) O of low-resistivity
xlaminated film (M is doping metals); At the upper and lower two-layer doped Ti O of deposition
yduring film, take Ar as sputter gas, at Ar, O
2in mist, Ar/O
2mist volume ratio is 4: 1 to 1: 4, and operating air pressure is 0.8-2Pa, and substrate is room temperature, simultaneously sputtered with Ti O
mtarget and doping metals or oxide target, sputtering power is 60-140W, and every layer of sputtering sedimentation is 0.5-2 hour, and sputtering sedimentation obtains (Ti, N) O of high resistivity
ylaminated film (N is doping metals, but from M can be different).
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| CN105869807A (en) * | 2016-05-03 | 2016-08-17 | 中国地质大学（北京） | Preparation method of zinc oxide-bismuth oxide thin film varistor |
| CN108218420A (en) * | 2017-05-25 | 2018-06-29 | 湖北文理学院 | A kind of titanium dioxide high pressure varistor and preparation method thereof |
| CN109536904A (en) * | 2018-12-10 | 2019-03-29 | 河南科技大学 | A kind of doping TiO2Barrier film and preparation method thereof |
| CN114807877A (en) * | 2021-01-19 | 2022-07-29 | 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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| CN105869807A (en) * | 2016-05-03 | 2016-08-17 | 中国地质大学（北京） | Preparation method of zinc oxide-bismuth oxide thin film varistor |
| CN108218420A (en) * | 2017-05-25 | 2018-06-29 | 湖北文理学院 | A kind of titanium dioxide high pressure varistor and preparation method thereof |
| CN109536904A (en) * | 2018-12-10 | 2019-03-29 | 河南科技大学 | A kind of doping TiO2Barrier film 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 |
| CN114807877A (en) * | 2021-01-19 | 2022-07-29 | 中国科学院上海硅酸盐研究所 | Black titanium dioxide photocatalytic film and preparation method and application 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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