CN101429643A - Low temperature production method of transparent conductive oxide film - Google Patents
Low temperature production method of transparent conductive oxide film Download PDFInfo
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- CN101429643A CN101429643A CNA2008102447156A CN200810244715A CN101429643A CN 101429643 A CN101429643 A CN 101429643A CN A2008102447156 A CNA2008102447156 A CN A2008102447156A CN 200810244715 A CN200810244715 A CN 200810244715A CN 101429643 A CN101429643 A CN 101429643A
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- 238000004519 manufacturing process Methods 0.000 title description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 239000010955 niobium Substances 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 71
- 238000000151 deposition Methods 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005137 deposition process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004549 pulsed laser deposition Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000000427 thin-film deposition Methods 0.000 claims description 4
- 229910002367 SrTiO Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 description 20
- 238000011160 research Methods 0.000 description 5
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010017472 Fumbling Diseases 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Abstract
The invention provides a low temperature preparation method for a transparent conductive oxide film. After a seed crystal layer is prepared through a pulsed laser method, niobium doped titanium oxide transparent conductive film material is prepared in succession respectively through the pulsed laser method or a magnetron sputtering method. The seed crystal layer can be anatase crystal type titanium oxide single-crystal. The thickness of the seed crystal layer is controlled at the length of c shafts of 0.5 to a plurality of unit cells. The titanium oxide base film material is continuously bred and prepared on the substrate material with the seed crystal layer through the pulsed laser method or the magnetron sputtering method. The preparation process has less dependency on the preparation technology and growing conditions. The preparation technology is flexible and is full of selectivity. The visible light transmission rate of the obtained titanium oxide base transparent conductive film is higher than 90 percent; and the resistivity at a room temperature is lower than 8x10<-4>ohm.cm. The method realizes the growth and preparation of the transparent conductive oxide film capable of replacing ITO.
Description
Technical field
The present invention relates to the low temperature preparation method of transparent conductive oxide film, belong to the photoelectricity information material technical field.
Background technology
Transparent conductive oxide (Transparent Conducting Oxide:TCO) film is meant the type oxide thin-film material to visible light (wavelength X=380-780nm) light transmission rate height (〉 80%), resistivity low (＜1 * 10-3 Ω cm).The TCO film is widely used in fields such as solar cell, screen display, photo-detector, window coating, low long wavelength laser, high-density storage, opticfiber communication at present.The research of current TCO film and application mainly concentrate on tin-doped indium oxide (Indium Tin Oxide:ITO) film.Because ito thin film has in characteristics such as visible region transmissivity height, infrared light reflection are strong, resistivity is low,, wear resistance strong with the sticking power of glass and chemical stability are good, has all formed the huge market scale in above-mentioned Application Areas.And along with improving constantly of science and technology development and living standards of the people, the widespread use of high resolving power and large size flat-panel screens and solar cell etc., market is more and more big to the demand of TCO film.The demand that is applied to the TCO thin-film material in the solar cell also will grow with each passing day.In recent years, be accompanied by the height enterprise and the approaching day by day phosphide element resource exhaustion problem of phosphide element price, people are are actively researching and developing the novel TCO thin-film material that is implemented on environmental friendliness and the aboundresources element strategic level.
The design and development of novel TCO film is round how making the better organic unity of light transmission and electroconductibility, can realizing its two unity of contradictions by bandgap structure, carrier concentration and mobility and the work function etc. of adjusting material on the principle.2005, people such as Furubayashi discovered niobium doped anatase phase TiO
2Thin-film material has good specific conductivity and visible light transmitance, epitaxially grown monocrystal thin films on the oxide monocrystal substrate, its every physical index all can compare favourably with the ITO material [Appl.Phys.Lett., Vol.86, pp.252101,2005].TiO
2Nonpoisonous and tasteless, the aboundresources of fertile material all is widely used in photochemical catalysis and dilute magnetic semiconductor.Simultaneously, TiO
2The more zno-based TCO thin-film material of base novel TCO thin-film material and present research is compared, and is with the obvious advantage aspect chemical stability.Yet, in the applied research and product development of reality, how in cheapness and grow TiO on stronger glass of practicality and the flexible substrate
2Base novel TCO thin-film material is a vital step.At present, external research in this respect is at the early-stage, the influence factor of each side is more, microscopic appearance and phase structure such as film, and the influence of oxygen double-void carrier mobility and optical parametric etc., cut-and-try work also is in stage of fumbling [Appl.Phys.Lett., Vol.90, pp.212106,2007].On the other hand, compare with sedimentary TCO film on the mechanically resistant material substrate, that the TCO film for preparing on flexible substrate has is in light weight, deflection, be difficult for broken, be easy to advantage such as big area production, can be applied to fields such as flexible substrate solar cell and flexible nano photoelectric device.And along with the microminiaturization and the lighting of electron device, the research of growth TCO film has caused people's extensive concern on the flexible substrate, is expected to become the renewal product of TCO film on the hard substrates.On flexible substrate, in the process of growth TCO film, need select for use higher substrate growth temperature or follow-up atmosphere heat treatment to guarantee the crystalline quality of TCO film usually.But the flexible substrate non-refractory is unfavorable for growing the TCO thin-film material with good photoelectricity performance, on preparation technology, for TCO growth for Thin Film process has increased difficult point, has proposed new challenge.
Therefore, the low temperature growth techniques of exploitation TCO film is expanded the application of TCO film in fields such as flexible substrate solar cell and is had high value and significance for improving the film preparation condition.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of low temperature preparation method of transparent conductive oxide film is provided.
Purpose of the present invention is achieved through the following technical solutions:
The low temperature preparation method of transparent conductive oxide film after employing pulse laser legal system is equipped with inculating crystal layer, adopts pulse laser method or magnetron sputtering method subsequent preparation niobium adulterated TiOx transparent conductive film material respectively again, and concrete steps are:
1. the growth of inculating crystal layer: after earlier the monocrystalline oxide substrate material being cleaned, and dry up, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control in the preparation process: underlayer temperature is 400～573K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 5～8J/cm
2, frequency is 3～8Hz, deposition O
2Dividing potential drop is 1 * 10
-2～1 * 10
-5Torr, target and substrate vertical spacing are 40mm～50mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out; Original position energetic reflection electron diffraction monitoring in real time shows: the inculating crystal layer structure is the titanium oxide monocrystalline of anatase crystal, and face is c axle orientation outward, and the inculating crystal layer film thickness is at 0.5～several structure cells c shaft length;
2. subsequent growth: adopt pulse laser method or magnetron sputtering method continued growth and the titania based transparent conductive film of preparation on the above-mentioned substrate material of preparing that has inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 2～8%; Wherein,
Adopt the pulse laser method: depositing temperature be room temperature to 473K, pulse-repetition 1～5Hz, laser energy density are 2～8J/cm
2, deposition O
2Dividing potential drop is 1 * 10
-2～1 * 10
-5Torr, target and substrate vertical spacing are 40mm～60mm, thin film deposition thickness is below 300 nanometers;
Adopt magnetron sputtering method: Ar gas and O
2Gas imports reaction chamber, Ar gas and O by conduit behind thorough mixing
2The flow-ratio control of gas is between 4～8, after treating that underlayer temperature is heated to the temperature range of 400～473K, sputter gas is introduced reaction chamber to the sediment chamber, after overall pressure reaches 1～10Pa, the beginning spatter film forming, sputtering power is controlled at 40～100W, and the vertical spacing of target and substrate is 50～100mm, and film thickness is controlled at below 300 nanometers;
After pulse laser method or magnetron sputtering method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.
Further, the low temperature preparation method of above-mentioned transparent conductive oxide film, monocrystalline oxide substrate material are SrTiO
3, or LaAlO
3, or SrLaAlO
4, or (LaAlO
3)
0.3(Sr
2AlTaO
6)
0.7
Further, the low temperature preparation method of above-mentioned transparent conductive oxide film, described monocrystalline oxide substrate material clean, clean, use at last the deionized water ultrasonic cleaning with ethanol again with acetone earlier, clean the back and dry up with nitrogen gun.
Again further, the low temperature preparation method of above-mentioned transparent conductive oxide film, the titania based transparent conductive film visible light transmissivity that is obtained is better than 90%, and room temperature resistivity is less than 8 * 10-4Ohm.cm.
Substantive distinguishing features and obvious improvement that technical solution of the present invention is outstanding are mainly reflected in:
The present invention adopts the inculating crystal layer of 0.5～several structure cells c shaft length to come the induced low temperature growth, obtains the titania based thin-film material with good clear electroconductibility.Inculating crystal layer is the titanium oxide monocrystalline of anatase crystal, adopts the pulse laser sediment method preparation, and gauge control is at 0.5～several structure cells c shaft length; Subsequently, having employing pulse laser method or magnetron sputtering method continued growth and the titania based thin-film material of preparation on the substrate material of inculating crystal layer, this preparation process is less to the dependency of preparation technology and growth conditions, preparation technology is flexible, is rich in selectivity, the titania based transparent conductive film visible light transmissivity that obtains is better than 90%, and room temperature resistivity is less than 8 * 10
-4Ohm.cm.The present invention realizes substituting low-temperature epitaxy and the preparation of ITO with transparent conductive oxide film, has greatly expanded the range of application of this type of material.
Description of drawings
Below in conjunction with accompanying drawing technical solution of the present invention is described further:
Fig. 1: inculating crystal layer process of growth original position energetic reflection electron diffraction is monitored collection of illustrative plates in real time;
Fig. 2 a: having the monocrystalline oxide substrate material (LaAlO of inculating crystal layer
3)
0.3(Sr
2AlTaO
6)
0.7The last titania based thin-film material that adopts pulse laser method continued growth and prepare;
Fig. 2 b: having the monocrystalline oxide substrate material (LaAlO of inculating crystal layer
3)
0.3(Sr
2AlTaO
6)
0.7The last titania based thin-film material that adopts the magnetron sputtering method continued growth and prepare.
Embodiment
Invention provides a kind of alternative ITO low temperature preparation method with transparent conductive oxide film, adopts the inculating crystal layer of 0.5～several structure cells c shaft length to come the induced low temperature growth, obtains the titania based thin-film material with good clear electroconductibility.
Below by specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
Earlier with monocrystalline oxide substrate material (SrTiO
3) clean, clean, use at last the deionized water ultrasonic cleaning with ethanol again with acetone, clean the back and dry up with nitrogen gun, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control: underlayer temperature is 400～450K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 5J/cm
2, frequency is 5Hz, deposition O
2Dividing potential drop is 1 * 10
-3Torr, target and substrate vertical spacing are 40mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out, and the inculating crystal layer film thickness is controlled at 0.5～several structure cells c shaft length;
Adopt the continued growth of pulse laser method to prepare titania based transparent conductive film having on the substrate material of inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 2%; Depositing temperature be room temperature to 473K, pulse-repetition 5Hz, laser energy density are 8J/cm
2, deposition O
2Dividing potential drop is 1 * 10
-3Torr, target and substrate vertical spacing are 60mm, the thin film deposition gauge control is below 300 nanometers; After pulse laser method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.Its film visible light transmissivity is better than 95%, room temperature resistivity 6.45 * 10-4Ohm.cm.
Embodiment 2:
Earlier with monocrystalline oxide substrate material (LaAlO
3) clean, clean, use at last the deionized water ultrasonic cleaning with ethanol again with acetone, clean the back and dry up with nitrogen gun, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control: underlayer temperature is 450～500K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 6J/cm
2, frequency is 8Hz, deposition O
2Dividing potential drop is 1 * 10
-2Torr, target and substrate vertical spacing are 50mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out, and the inculating crystal layer film thickness is controlled at 0.5～several structure cells c shaft length;
Having continued growth of employing pulse laser method and the titania based transparent conductive film of preparation on the substrate material of inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 4%; Depositing temperature be room temperature to 473K, pulse-repetition 1Hz, laser energy density are 2J/cm
2, deposition O
2Dividing potential drop is 1 * 10
-2Torr, target and substrate vertical spacing are 40mm, the thin film deposition gauge control is below 300 nanometers; After pulse laser method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.Its film visible light transmissivity is for being better than 93%, room temperature resistivity 7.15 * 10-4Ohm.cm.
Embodiment 3:
Earlier with monocrystalline oxide substrate material (SrLaAlO
4) clean, clean, use at last the deionized water ultrasonic cleaning with ethanol again with acetone, clean the back and dry up with nitrogen gun, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control: underlayer temperature is 420～480K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 7J/cm
2, frequency is 3Hz, deposition O
2Dividing potential drop is 1 * 10
-4Torr, target and substrate vertical spacing are 45mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out, and the inculating crystal layer film thickness is controlled at 0.5～several structure cells c shaft length;
Adopt the magnetron sputtering method continued growth to prepare titania based transparent conductive film having on the substrate material of inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 6%; Ar gas and O
2Gas imports reaction chamber, Ar gas and O by conduit behind thorough mixing
2(Ar gas is 24sccm, O 4 in the flow-ratio control of gas
2Be 6sccm), after treating that underlayer temperature is heated to the temperature range of 400～473K, sputter gas is introduced reaction chamber to the sediment chamber, after overall pressure reaches 1～10Pa, the beginning spatter film forming, sputtering power is controlled at 100W, and the vertical spacing of target and substrate is 50mm, and film thickness is controlled at below 300 nanometers; After magnetron sputtering method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.Its film visible light transmissivity is for being better than 90%, room temperature resistivity 7.46 * 10-4Ohm.cm.
Embodiment 4:
Earlier with monocrystalline oxide substrate material ((LaAlO
3)
0.3(Sr
2AlTaO
6)
0.7) clean, clean, use at last the deionized water ultrasonic cleaning with ethanol again with acetone, clean the back and dry up with nitrogen gun, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control: underlayer temperature is 500～573K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 8J/cm
2, frequency is 3Hz, deposition O
2Dividing potential drop is 1 * 10
-5Torr, target and substrate vertical spacing are 50mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out, and the inculating crystal layer film thickness is controlled at 0.5～several structure cells c shaft length;
Adopt the magnetron sputtering method continued growth to prepare titania based transparent conductive film having on the substrate material of inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 8%; Ar gas and O
2Gas imports reaction chamber, Ar gas and O by conduit behind thorough mixing
2(Ar gas is 24sccm, O 8 in the flow-ratio control of gas
2Be 3sccm), after treating that underlayer temperature is heated to the temperature range of 400～473K, sputter gas is introduced reaction chamber to the sediment chamber, after overall pressure reaches 1～10Pa, the beginning spatter film forming, sputtering power is controlled at 40W, and the vertical spacing of target and substrate is 100mm, and film thickness is controlled at below 300 nanometers; After magnetron sputtering method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.Its film visible light transmissivity is for being better than 90%, room temperature resistivity 7.69 * 10-4Ohm.cm.
Fig. 1 has illustrated inculating crystal layer process of growth original position energetic reflection electron diffraction to monitor collection of illustrative plates in real time; Fig. 2 a has illustrated having the monocrystalline oxide substrate material (LaAlO of inculating crystal layer
3)
0.3(Sr
2AlTaO
6)
0.7The last titania based thin-film material that adopts pulse laser method continued growth and prepare; Fig. 2 b has illustrated having the monocrystalline oxide substrate material (LaAlO of inculating crystal layer
3)
0.3(Sr
2AlTaO
6)
0.7The last titania based thin-film material that adopts the magnetron sputtering method continued growth and prepare.
In sum, the present invention adopts the inculating crystal layer of 0.5～several structure cells c shaft length to come the induced low temperature growth, obtains the titania based thin-film material with good clear electroconductibility.Inculating crystal layer is the titanium oxide monocrystalline of anatase crystal, adopts the pulse laser sediment method preparation earlier, and gauge control is at 0.5～several structure cells c shaft length; Subsequently, having employing pulse laser method or magnetron sputtering method continued growth and the titania based thin-film material of preparation on the substrate material of inculating crystal layer, this preparation process is less to the dependency of preparation technology and growth conditions, preparation technology is flexible, is rich in selectivity, the titania based transparent conductive film visible light transmissivity that obtains is better than 90%, and room temperature resistivity is less than 8 * 10-4ohm.cm.The present invention realizes substituting low-temperature epitaxy and the preparation of ITO with transparent conductive oxide film, has greatly expanded the range of application of this type of material.
What need understand is: above-mentioned explanation is not to be limitation of the present invention, and in the present invention conceived scope, the interpolation of being carried out, conversion, replacement etc. also should belong to protection scope of the present invention.
Claims (4)
1. the low temperature preparation method of transparent conductive oxide film is characterized in that: specifically may further comprise the steps---
1. the growth of inculating crystal layer: after earlier the monocrystalline oxide substrate material being cleaned, and dry up, put into vacuum chamber immediately, reaction chamber back of the body end absolute pressure is lower than 1 * 10 before the deposition
-5Torr; With sintered ceramic TiO
2Sheet is as target, is better than 99.99% O with purity
2As deposition atmosphere, adopt pulsed laser deposition to prepare the inculating crystal layer film, control in the preparation process: underlayer temperature is 400～573K, back of the body end absolute pressure is lower than 5 * 10
-4Torr, laser energy density are 5～8J/cm
2, frequency is 3～8Hz, deposition O
2Dividing potential drop is 1 * 10
-2～1 * 10
-5Torr, target and substrate vertical spacing are 40mm～50mm; Deposition process cools to room temperature with the furnace after finishing, and behind the cut-out oxygen, takes out, and the inculating crystal layer film thickness is at 0.5～several structure cells c shaft length;
2. subsequent growth: adopt pulse laser method or magnetron sputtering method continued growth and the titania based transparent conductive film of preparation on the above-mentioned substrate material of preparing that has inculating crystal layer, underlayer temperature is controlled at the following low-temperature zone of 473K, and its target composition is Nb
2O
5-TiO
2, niobium is at TiO
2Middle atomic percentage conc accounts for 2～8%; Wherein,
Adopt the pulse laser method: depositing temperature be room temperature to 473K, pulse-repetition 1～5Hz, laser energy density are 2～8J/cm
2, deposition O
2Dividing potential drop is 1 * 10
-2～1 * 10
-5Torr, target and substrate vertical spacing are 40mm～60mm, thin film deposition thickness is below 300 nanometers;
Adopt magnetron sputtering method: Ar gas and O
2Gas imports reaction chamber, Ar gas and O by conduit behind thorough mixing
2The flow-ratio control of gas is between 4～8, after treating that underlayer temperature is heated to the temperature range of 400～473K, sputter gas is introduced reaction chamber to the sediment chamber, after overall pressure reaches 1～10Pa, the beginning spatter film forming, sputtering power is controlled at 40～100W, and the vertical spacing of target and substrate is 50～100mm, and film thickness is controlled at below 300 nanometers;
After pulse laser method or magnetron sputtering method deposition is finished, all cool to room temperature with the furnace after, cut off gas source, take out, obtain titania based transparent conductive film.
2. the low temperature preparation method of transparent conductive oxide film according to claim 1, it is characterized in that: the monocrystalline oxide substrate material is SrTiO
3, or LaAlO
3, or SrLaAlO
4, or (LaAlO
3)
0.3(Sr
2AlTaO
6)
0.7
3. the low temperature preparation method of transparent conductive oxide film according to claim 1 and 2, it is characterized in that: described monocrystalline oxide substrate material cleans, cleans, uses at last the deionized water ultrasonic cleaning with ethanol again with acetone earlier, cleans the back and dries up with nitrogen gun.
4. the low temperature preparation method of transparent conductive oxide film according to claim 1, it is characterized in that: the titania based transparent conductive film visible light transmissivity that is obtained is better than 90%, and room temperature resistivity is less than 8 * 10-4Ohm.cm.
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|---|---|---|---|
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|---|---|---|---|
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| CN102312192A (en) * | 2010-06-30 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof |
| CN102560399A (en) * | 2012-01-09 | 2012-07-11 | 中国矿业大学 | Preparation method for erbium-ytterbium-doped polycrystalline oxide film |
| CN103072341A (en) * | 2013-01-22 | 2013-05-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass and sandwich glass product thereof |
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| CN105895807A (en) * | 2016-05-06 | 2016-08-24 | 郑州大学 | Preparation method of TiO2-dopted film |
| CN106191775A (en) * | 2015-09-18 | 2016-12-07 | 北京大学深圳研究生院 | A kind of transparent conductive film and its preparation method and application |
| CN108103466A (en) * | 2017-12-21 | 2018-06-01 | 君泰创新（北京）科技有限公司 | The preparation method of high mobility transparent conductive oxide film |
| US10103282B2 (en) | 2016-09-16 | 2018-10-16 | Nano And Advanced Materials Institute Limited | Direct texture transparent conductive oxide served as electrode or intermediate layer for photovoltaic and display applications |
| CN109082631A (en) * | 2018-07-13 | 2018-12-25 | 华南师范大学 | A kind of Ga2O3Base transparent conducting film and preparation method thereof |
| CN112119128A (en) * | 2018-05-16 | 2020-12-22 | 默克专利股份有限公司 | Laser additives and their use in polymeric materials |
| CN114775043A (en) * | 2022-04-20 | 2022-07-22 | 中国科学院半导体研究所 | Preparation method for improving film thickness uniformity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102312192B (en) * | 2010-06-30 | 2013-07-17 | 中国科学院上海硅酸盐研究所 | Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof |
| CN102312192A (en) * | 2010-06-30 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof |
| CN102560399A (en) * | 2012-01-09 | 2012-07-11 | 中国矿业大学 | Preparation method for erbium-ytterbium-doped polycrystalline oxide film |
| CN102560399B (en) * | 2012-01-09 | 2013-06-05 | 中国矿业大学 | Preparation method for erbium-ytterbium-doped polycrystalline oxide film |
| CN103072341A (en) * | 2013-01-22 | 2013-05-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass and sandwich glass product thereof |
| CN103088295A (en) * | 2013-01-28 | 2013-05-08 | 湖北大学 | Preparation method of vanadium-gallium codoped titanium oxide film with great red shift and high absorbability |
| CN103956261A (en) * | 2014-04-22 | 2014-07-30 | 河北大学 | Nano-structure multifunctional ferromagnetic composite film material and preparation method |
| CN103956261B (en) * | 2014-04-22 | 2016-03-30 | 河北大学 | The multi-functional ferromagnetic composite film material of nanostructure and preparation method |
| CN106191775A (en) * | 2015-09-18 | 2016-12-07 | 北京大学深圳研究生院 | A kind of transparent conductive film and its preparation method and application |
| CN105895807A (en) * | 2016-05-06 | 2016-08-24 | 郑州大学 | Preparation method of TiO2-dopted film |
| CN105895807B (en) * | 2016-05-06 | 2018-11-16 | 郑州大学 | A kind of doping TiO2The preparation method of film |
| US10103282B2 (en) | 2016-09-16 | 2018-10-16 | Nano And Advanced Materials Institute Limited | Direct texture transparent conductive oxide served as electrode or intermediate layer for photovoltaic and display applications |
| CN108103466A (en) * | 2017-12-21 | 2018-06-01 | 君泰创新（北京）科技有限公司 | The preparation method of high mobility transparent conductive oxide film |
| CN112119128A (en) * | 2018-05-16 | 2020-12-22 | 默克专利股份有限公司 | Laser additives and their use in polymeric materials |
| CN112119128B (en) * | 2018-05-16 | 2022-03-01 | 默克专利股份有限公司 | Laser additives and their use in polymeric materials |
| CN109082631A (en) * | 2018-07-13 | 2018-12-25 | 华南师范大学 | A kind of Ga2O3Base transparent conducting film and preparation method thereof |
| CN114775043A (en) * | 2022-04-20 | 2022-07-22 | 中国科学院半导体研究所 | Preparation method for improving film thickness uniformity |
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