CN108364853A - A kind of flexible metal substrate and its preparation method and application - Google Patents
A kind of flexible metal substrate and its preparation method and application Download PDFInfo
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- CN108364853A CN108364853A CN201810087557.1A CN201810087557A CN108364853A CN 108364853 A CN108364853 A CN 108364853A CN 201810087557 A CN201810087557 A CN 201810087557A CN 108364853 A CN108364853 A CN 108364853A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 148
- 239000002184 metal Substances 0.000 title claims abstract description 148
- 239000000758 substrate Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000010409 thin film Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000011888 foil Substances 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 14
- 238000002161 passivation Methods 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004642 Polyimide Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 16
- 229910052735 hafnium Inorganic materials 0.000 claims 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 2
- 230000003139 buffering effect Effects 0.000 claims 1
- 239000011241 protective layer Substances 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000001755 magnetron sputter deposition Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 238000000231 atomic layer deposition Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000001259 photo etching Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229960001296 zinc oxide Drugs 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- IUZNJVILEJRNNP-UHFFFAOYSA-N magnesium;oxozinc Chemical compound [Mg].[Zn]=O IUZNJVILEJRNNP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02425—Conductive materials, e.g. metallic silicides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/02428—Structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66969—Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
- H01L29/861—Diodes
- H01L29/8611—Planar PN junction diodes
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Thin Film Transistor (AREA)
Abstract
The present invention provides a kind of flexible metal substrate for making flexible thin-film transistor or thin film diode, the flexible metal substrate includes metal foil and the coat of metal that is attached on the metal foil surface, wherein, when being observed under 10 × 10 μm of scanning range by atomic force microscope, the r.m.s. roughness of the flexible metal substrate<10nm.The present invention prepares flexible thin-film transistor or thin film diode using metal as substrate, efficiently solves the problems, such as that existing organic flexible substrate cannot bear high-temperature process.In conjunction with high-temperature thermal annealing technique, the electric property and stability of thin film transistor (TFT) and diode can greatly improve.The heat that the high heat conductance of metal substrate distributes when can also be by transistor and diode operation conducts in time, eliminates influence of the fuel factor to device, further improves its performance and stability.
Description
Technical field
The present invention relates to flexible electronic device field, especially a kind of flexible metal substrate and preparation method thereof and in film
Application in transistor and thin film diode.
Background technology
In recent years, flexible electronic material and device based on flexible substrate have received widespread attention, Flexible Displays, can
The correlative study in the fields such as wearable device, Internet of Things, medical treatment electronic equipment and defence equipment achieves development at full speed.It wants
Realize the practical application of Technology of Flexibility, thin film transistor (TFT) and thin film diode flexible are two indispensable critical electronic devices
Part.Flexible thin-film transistor is the important component of flexible electronic device, wherein thin as the Zinc oxide-base of representative using InGaZnO
Film transistor is in Flexible Displays market in occupation of increasingly consequence；On the other hand, Chinese patent
No.201710718914.5 discloses a kind of flexible field-effect diode, which can tolerate high pressure, have high commutating ratio,
The blank of flexible high pressure devices field is filled up.However, there are still many urgently to be resolved hurrily in commercialization process for the two at present
Problem, wherein performance degradation caused by dependence and device spontaneous heating with device performance to high-temperature process is the most key.
By taking zinc oxide as an example, preparation method mainly has solwution method and vacuum deposition method two major classes.Solwution method includes mainly
Sol-gal process and spray pyrolysis etc., it is thick that prepared zinc-oxide film needs high-temperature post-treatment (being usually above 300 DEG C)
Change and removal of impurity.The performance of zinc oxide thin-film transistor prepared by vacuum deposition method is very sensitive to oxygen content, growth window
It is very narrow, it is therefore desirable to which that thermal annealing regulates and controls the oxygen content in zinc oxide.Particularly, high annealing can significantly improve zinc oxide
The stability of based thin film transistors.However, current flexible substrate is based on organic polymer, such as polyimides (PI), poly- pair
Ethylene terephthalate (PET), polyethylene naphthalate (PEN).Their flexibilities are good, operability is strong, but right
The poor air-tightness of water and oxygen, the adhesion strength between inorganic material is small, affects the performance and stability of device.The most key
It is that their glass transition temperature is low, it is difficult to higher temperature is born, thus required high-temperature post-treatment process can not be carried out, it is difficult
To obtain excellent performance and good stability.
On the other hand, thin film transistor (TFT), diode will produce Joule heat and hot carrier's effect at work, in active layer
It nearby will produce a large amount of heat.General organic flexible substrate thermal conductivity very little, if the thermal conductivity of PI substrates is 0.12Wm-1·K-1, it is difficult in time heat caused by active layer when work is transferred out, so that the temperature near active layer
It dramatically increases, the performance of device is degenerated due to spontaneous heating.
It can effectively be solved the above problems using flexible metal as the substrate of device.Metal substrate can completely cut off well
Water and oxygen can bear high-temperature process.Its high heat conductance helps to realize rapid cooling, thus can improve flexible electronic device
The stability and service life of part.But the general surface of metal substrate for flexible electronic device is very coarse, root mean square
Roughness is at hundreds of nanometers or more.Pass through the metal foil also trace with rolling of roll forming.Chinese patent
No.200910194558.7 discloses a kind of precise polishing method at stainless steel lining bottom, and this method will using chemically mechanical polishing
The r.m.s. roughness at stainless steel lining bottom is down to 0.7nm.Chinese patent No.201110191555.5 discloses a kind of for flexibility
The substrate of display device and the method for preparing the substrate, this method inorganic material layer and organic material layer on metal substrate
To realize surface planarisation.However, precise polished prohibitively expensive for large-sized flexible electronic device.In addition, using
Organic polymer reduces surface roughness there is also cannot bear high-temperature process as flatness layer, and inorganic material is made
Larger thickness, substrate is needed to easy to produce crackle or stripping when being bent, the flexibility of device can be influenced for flatness layer.
Invention content
Therefore, it is an object of the invention to solve the above problems, provides a kind of for making flexible thin-film transistor and thin
The flexible metal substrate of film diode, the substrate have low surface roughness.
It is a further object to provide a kind of methods making flexible thin-film transistor and thin film diode, use
Low-cost simple process makes the low flexible metal substrate of surface roughness, makes thin film transistor (TFT) and thin over the substrate
Film diode can bear high-temperature process, reduce the influence of fuel factor, so as to produce high performance fexible film crystal
Pipe and thin film diode.
A further object of the present invention is to provide a kind of flexible thin-film transistor based on metal substrate.
It is also another object of the present invention to provide a kind of fexible film diode based on metal substrate.
According to the first aspect of the invention, it provides a kind of for making flexible thin-film transistor or thin film diode
Flexible metal substrate, the flexible metal substrate include metal foil and the coat of metal that is attached on the metal foil surface,
Wherein, when being observed under 10 × 10 μm of scanning range by atomic force microscope, the root mean square of the flexible metal substrate is thick
Rugosity<10nm.
In some embodiments of the present invention, the r.m.s. roughness of the flexible metal substrate is 0.5~9.9nm.
Preferably, the thickness of the metal foil is 5~125 μm, and the thickness of the coat of metal is 1~25 μm.
According to flexible metal substrate provided by the invention, wherein the metal foil can be Ag, Al, Au, Co, Cr,
It is one or more in Cu, Fe, Ir, Mo, Ni, Pb, Pd, Pt, Rh, Ru, Sn, Ta, Ti, V, W, Zr and stainless steel (SUS), it is described
Electroplated metal layer can be one or more in Ag, Au, Cd, Co, Cr, Cu, Ir, Ni, Pb, Pd, Pt, Rh, W and Zn.It is described
The metal of metal foil and the electroplated metal layer may be the same or different, this is not particularly limited in the present invention.
According to the second aspect of the invention, the preparation method of above-mentioned flexible metal substrate is additionally provided, the preparation method packet
It includes：Using galvanoplastic the coat of metal is formed in metal foil.
Preferably, the galvanoplastic include：Clean metal foil, the pollutants such as removal organic attachment in surface；By metal foil
Piece is positioned over the cathode site in electroplating bath, and anode is metal material to be plated, and electroplate liquid is added in electroplating bath；In cathode
Apply electric current and voltage between anode, current range is 0.1~1A, and voltage range is 1~10V；Plating a period of time obtains institute
It takes out, clean and dries up after needing thickness.
According to the third aspect of the invention we, a kind of flexible thin-film transistor, the flexible thin-film transistor packet are additionally provided
It includes：Flexible metal substrate, buffer protection layer, channel layer, gate insulation layer, gate electrode, source electrode, drain electrode and passivation layer, wherein
The flexible metal substrate is for flexible metal substrate provided by the invention or by flexible metal substrate made from the method for the present invention.
According to flexible thin-film transistor provided by the invention, wherein cover buffer protection in the flexible metal substrate
Layer, effect are that metal substrate and gate electrode, source electrode and drain electrode insulate.
According to the fourth aspect of the invention, a kind of fexible film diode, the fexible film diode packet are additionally provided
It includes：Flexible metal substrate, buffer protection layer, channel layer, insulating layer, first electrode, second electrode, connection electrode and passivation layer,
The wherein described flexible metal substrate is for flexible metal substrate provided by the invention or by flexible metal made from the method for the present invention
Substrate.
According to flexible thin-film transistor provided by the invention, wherein cover buffer protection in the flexible metal substrate
Layer, effect are that metal substrate and first electrode, second electrode and connection electrode insulate.
According to flexible thin-film transistor provided by the invention or fexible film diode, wherein the buffer protection layer can
Think inorganic insulating material or organic polymer insulating materials.For example, the material of the buffer protection layer can be aluminium oxide
(Al2O3), hafnium oxide (HfO2), silica (SiOx), silicon nitride (SiNx), titanium oxide (TiO2), yttrium oxide (Y2O3), polyamides it is sub-
It is one or more in amine and polytetrafluoroethylene (PTFE).In a kind of specific embodiment of the present invention, the material of the buffer protection layer
Material can be the mixture of polyimides and polytetrafluoroethylene (PTFE).Preferably, the thickness of the buffer protection layer can be for 100nm extremely
1μm。
According to the fifth aspect of the invention, a kind of flexible thin-film transistor or fexible film diode of making is additionally provided
Method the described method comprises the following steps：Galvanoplastic are used to form the coat of metal in metal foil to prepare flexible metal substrate；
Buffer protection layer is deposited in the flexible metal substrate；Two pole of thin film transistor (TFT) or film is prepared on the buffer protection layer
Pipe is to form the flexible thin-film transistor or fexible film diode based on metal substrate.
The present invention prepares flexible thin-film transistor or thin film diode using metal as substrate, efficiently solves existing
Organic flexible substrate the problem of cannot bearing high-temperature process.In conjunction with high-temperature thermal annealing technique, thin film transistor (TFT) and diode
Electric property and stability can greatly improve.The high heat conductance of metal substrate dissipates when can also be by transistor and diode operation
The heat of hair conducts in time, eliminates influence of the fuel factor to device, further improves its performance and stability.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：
Fig. 1 is the flow chart that the present invention prepares thin film transistor (TFT) or thin film diode on the metallic substrate.
Fig. 2 is the diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 1.
Fig. 3 is the simulation model schematic diagram and analog result figure of the embodiment of the present invention 1.
Fig. 4 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 2.
Fig. 5 is the transfer characteristic curve before and after thin film transistor (TFT) prepared by embodiment 2 is annealed at 300 DEG C.
Fig. 6 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 3.
Fig. 7 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 4.
Fig. 8 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 5.
Fig. 9 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 6.
Figure 10 is the schematic top plan view and diagrammatic cross-section of thin film transistor (TFT) prepared by embodiment 7.
Figure 11 is the schematic top plan view and diagrammatic cross-section of thin film diode prepared by embodiment 8.
Specific implementation mode
The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining
The bright present invention, the range being not intended to be limiting of the invention.
Fig. 1 is a kind of exemplary implementation scheme according to the present invention, prepares thin film transistor (TFT) or film on the metallic substrate
The flow chart of diode.As shown in Figure 1, step 1：The higher copper metal paillon of surface roughness 101 is cleaned up；Step
Two：Cu metals 102 are electroplated on shaggy Cu metal foils 101, to improve its roughness, form flexible metal substrate；
Step 3：Technique for atomic layer deposition (ALD) depositing Al is used in flexible metal substrate2O3Buffer protection layer 103；Step 4：
Al2O3Thin film transistor (TFT) or thin film diode 104 are made on buffer protection layer 103, and it is brilliant to obtain the film based on flexible metal substrate
Body pipe or thin film diode.
Embodiment 1
The present embodiment is prepared for a kind of thin film transistor (TFT) using metal substrate.
Fig. 2 is the diagrammatic cross-section of thin film transistor (TFT) manufactured in the present embodiment.As shown in Fig. 2, in the Ni metal of 30 μ m-thicks
The Al of ALD deposition 150nm thickness is used on substrate 2012O3Buffer protection layer 202, in Al2O3Film is prepared on buffer protection layer 202
Transistor 203 obtains the thin film transistor (TFT) based on flexible metal substrate.
Wherein, the preparation method of the Ni metal substrate 201 is as follows：
The Cu that 5 μ m-thicks are electroplated on the Ni metal with rough surface of 25 μ m-thicks obtains Ni metal substrate 201, and anode is
Metallic copper, electroplate liquid are copper-bath, electric current 0.25A, voltage 2V.
Fig. 3 is the simulation model schematic diagram and analog result figure of thin film transistor (TFT) manufactured in the present embodiment.By film crystal
The fever of pipe is reduced to heat source Q=5 × 108W/m2, the lateral edges temperature of copper substrate is set as 293.15K, all boundaries all with sky
Thermal convection current occurs for gas, and the initial temperature of air is set as 293.15K.Compare Cu substrates and Si substrate temperatures under the same terms
Distribution, obtains the maximum temperature for using Cu substrate film transistors as 323.56K, the model that can be still worked normally in general device
Within enclosing；And use Si substrates then for 382.12K, it is much larger than the temperature tolerance range of general device.
Embodiment 2
The present embodiment is prepared for the device architecture of the thin film transistor (TFT) using metal substrate, and structure type is overlapping for bottom gate
Type.
Fig. 4 is schematic top plan view and the section signal of the thin film transistor (TFT) 300 manufactured in the present embodiment using metal substrate
Figure.As shown in figure 4, thin film transistor (TFT) 300 includes Ni metal substrate 301, Al successively from top to bottom2O3Buffer protection layer 302, Cr
Gate electrode 303, HfO2Gate insulation layer 304, ZnO channel layers 305, indium tin oxygen (ITO) source electrode and drain electrode 306, SiO2Passivation layer
307。
The preparation method of the thin film transistor (TFT) is as follows：
The Cu that 1 μ m-thick is electroplated on the Ni metal with rough surface of 5 μ m-thicks obtains Ni metal substrate 301, and anode is
Metallic copper, electroplate liquid are copper-bath, electric current 0.15A, voltage 1V.
The Al of 100nm thickness is prepared using ALD on the Ni metal substrate 301 of 6 μ m-thicks2O3Buffer protection layer 302；Using magnetic
Control sputtering technology prepares the Cr gate electrodes 303 of 100nm thickness；The HfO of 50nm thickness is prepared using ALD2Gate insulation layer 304；Using magnetic
Control sputtering technology prepares the ZnO channel layers 305 of 50nm thickness, then passes through photoetching and salt acid etch, and figure is carried out to channel layer 305
Change is handled；The ITO source electrode and drain electrodes 306 of 50nm thickness are prepared using magnetron sputtering technique；Using plasma enhancing chemistry
Gas phase deposition technology (PECVD) prepares the SiO of 100nm thickness2Passivation layer 307.
Fig. 5 is the transfer characteristic curve before and after the thin film transistor (TFT) of metal substrate manufactured in the present embodiment is annealed at 300 DEG C
Figure.It wherein sets drain voltage to 1V, while grid voltage is scanned from -10V to 20V.As can be seen that device after annealing
The performance of part, which has, to be substantially improved.
Embodiment 3
The present embodiment is prepared for a kind of device architecture of the thin film transistor (TFT) using metal substrate, and structure type is bottom gate
Coplanar type.
Fig. 6 is that the schematic top plan view figure of the thin film transistor (TFT) 400 manufactured in the present embodiment using metal substrate and section show
It is intended to.As shown in fig. 6, thin film transistor (TFT) 400 includes metal substrate 401, SiO successively from top to bottom2Buffer protection layer 402, Al
Gate electrode 403, Al2O3Gate insulation layer 404, Au source electrode and drain electrodes 405, IGZO channel layers 406, silicon nitride (Si3N4) passivation
Layer 407.
The preparation method of the thin film transistor (TFT) is as follows：
The Ag that 25 μ m-thicks are electroplated on the metal SUS with rough surface of 100 μ m-thicks obtains flexible compound metal substrate
401, anode is metal Ag, and electroplate liquid is silver potassium cyanide solution, electric current 0.2A, voltage 3V.
The SiO of 1 μ m-thick is prepared using PECVD in the flexible compound metal substrate 401 of 125 μ m-thicks2Buffer protection layer
402；The Al gate electrodes 403 of 80nm thickness are prepared using magnetron sputtering technique；The Al of 60nm thickness is prepared using ALD2O3Gate insulation layer
404；The Au source electrode and drain electrodes 405 of 50nm thickness are prepared using thermal evaporation techniques；It is thick that 30nm is prepared using magnetron sputtering technique
IGZO channel layers 406, then pass through photoetching and salt acid etch, processing is patterned to channel layer 406；Using PECVD systems
The Si of standby 150nm thickness3N4Passivation layer 407.
Device is tested using method same as Example 2, obtains similar as a result, there is performance after annealing
It is substantially improved.
Embodiment 4
The present embodiment is prepared for a kind of device architecture of the thin film transistor (TFT) using metal substrate, and structure type is top-gated
Overlapping type.
The schematic top plan view figure and section of Fig. 7 thin film transistor (TFT)s 500 manufactured in the present embodiment using metal substrate are illustrated
Figure.As shown in fig. 7, thin film transistor (TFT) 500 includes SUS substrates 501, Si successively from top to bottom3N4Buffer protection layer 502, the sources Al electricity
Pole and drain electrode 503, ZnO channel layers 504, zirconium oxide (ZrO2) gate insulation layer 505, Mo gate electrodes 506.
The preparation method of the thin film transistor (TFT) is as follows：
The Cr that 10 μ m-thicks are electroplated on the metal SUS with rough surface of 40 μ m-thicks obtains flexible compound metal substrate
501, anode is metal Pb, and electroplate liquid is chromic anhydride and sulfuric acid mixed solution, electric current 1A, voltage 10V.
The Si of 250nm thickness is prepared using PECVD in the flexible compound metal substrate 501 of 50 μ m-thicks3N4Buffer protection layer
502；The Al source electrode and drain electrodes 503 of 90nm thickness are prepared using magnetron sputtering technique；40nm is prepared using magnetron sputtering technique
Then thick ZnO channel layers 504 pass through photoetching and salt acid etch, processing are patterned to channel layer 504；It is splashed using magnetic control
The technology of penetrating prepares the ZrO of 50nm thickness2Gate insulation layer 505；The Mo gate electrodes 506 of 100nm thickness are prepared using electron beam evaporation technique.
Device is tested using method same as Example 2, obtains similar as a result, there is performance after annealing
It is substantially improved.
Embodiment 5
The present embodiment is prepared for a kind of device architecture of the thin film transistor (TFT) using metal substrate, and structure type is top-gated
Coplanar type.
The schematic top plan view figure and section of Fig. 8 thin film transistor (TFT)s 600 manufactured in the present embodiment using metal substrate are illustrated
Figure.As shown in figure 8, thin film transistor (TFT) 600 includes metal Ag substrates 601, TiO successively from top to bottom2Buffer protection layer 602, magnesium
Zinc oxygen (MZO) channel layer 603, Cu source electrode and drain electrodes 604, yttrium oxide (Y2O3) gate insulation layer 605, Ni gate electrodes 606.
The preparation method of the thin film transistor (TFT) is as follows：
The Ag that 2 μ m-thicks are electroplated on the metal Ag with rough surface of 8 μ m-thicks obtains the metal Ag substrates of 10 μ m-thicks
601, anode is metal Ag, and electroplate liquid is silver potassium cyanide solution, electric current 0.15A, voltage 2V.
The TiO of 200nm thickness is prepared using magnetron sputtering technique on the Ag substrates 601 of 10 μ m-thicks2Buffer protection layer 602；
The MZO channel layers 603 of 50nm thickness are prepared using magnetron sputtering technique, then pass through photoetching and salt acid etch, to channel layer 603 into
Row graphical treatment；The Cu source electrode and drain electrodes 604 of 50nm thickness are prepared using thermal evaporation techniques；Using magnetron sputtering technique system
The Y of standby 50nm thickness2O3Gate insulation layer 605；The Ni gate electrodes 606 of 100nm thickness are prepared using magnetron sputtering technique.
Device is tested using method same as Example 2, obtains similar as a result, there is performance after annealing
It is substantially improved.
Embodiment 6
The present embodiment is prepared for a kind of device architecture of the thin film transistor (TFT) using metal substrate, the device architecture and implementation
Device architecture is similar described in example 1, and difference lies in use circular electrode shape.
Fig. 9 is that the schematic top plan view figure of the thin film transistor (TFT) 700 manufactured in the present embodiment using metal substrate and section show
It is intended to.As shown in figure 9, thin film transistor (TFT) 700 includes Pt metal substrate 701, polyimides buffer protection layer successively from top to bottom
702, Ti gate electrodes 703, Al2O3Gate insulation layer 704, IGZO channel layers 705, Pd source electrodes 706 and Pd drain electrodes 707, SiO2It is blunt
Change layer 708.
The preparation method of the thin film transistor (TFT) is as follows：
The Pt that 10 μ m-thicks are electroplated on the Pt metal with rough surface of 20 μ m-thicks obtains the Pt metal substrate of 30 μ m-thicks
701, anode is Pt metal, and electroplate liquid is platinum acid chloride solution, electric current 0.3A, voltage 3V.
The polyimides buffer protection layer of 700nm thickness is prepared using spin coating method on the Pt metal substrate 701 of 30 μ m-thicks
702；The Ti gate electrodes 703 of 100nm thickness are prepared using magnetron sputtering technique；The Al of 70nm thickness is prepared using ALD2O3Gate insulation layer
704；The IGZO channel layers 705 of 50nm thickness are prepared using magnetron sputtering technique, then pass through photoetching and salt acid etch, to channel layer
705 are patterned processing；The Pd source electrodes 706 and Pd drain electrodes 707 of 70nm thickness are prepared using magnetron sputtering technique；Using
PECVD prepares the SiO of 100nm thickness2Passivation layer 708.
Device is tested using method same as Example 2, obtains similar as a result, there is performance after annealing
It is substantially improved.
Embodiment 7
The present embodiment is prepared for a kind of device architecture of the thin film transistor (TFT) using metal substrate, the device architecture and implementation
Device architecture is similar described in example 1, and difference lies in there is wrong row region between gate electrode and source electrode and drain electrode.
Figure 10 is that the schematic top plan view figure of the thin film transistor (TFT) 800 manufactured in the present embodiment using metal substrate and section show
It is intended to.As shown in Figure 10, thin film transistor (TFT) 800 includes metal Au substrates 801, Al successively from top to bottom2O3Buffer protection layer 802,
Ag gate electrodes 803, HfO2Gate insulation layer 804, ZnO channel layers 805, Mo source electrode and drain electrodes 806, Si3N4Passivation layer 807.
The preparation method of the thin film transistor (TFT) is as follows：
The Au that 5 μ m-thicks are electroplated on the metal Au with rough surface of 15 μ m-thicks obtains the metal Au substrates of 20 μ m-thicks
801, anode is Pt metal, and electroplate liquid is potassium auricyanide solution, electric current 0.25A, voltage 4V.
The Al of 250nm thickness is prepared using ALD on the metal Au substrates 801 of 20 μ m-thicks2O3Buffer protection layer 802；Using heat
Evaporation technique prepares the Ag gate electrodes 803 of 50nm thickness；The HfO of 80nm thickness is prepared using ALD2Gate insulation layer 804；It is splashed using magnetic control
The technology of penetrating prepares the ZnO channel layers 805 of 40nm thickness, then passes through photoetching and salt acid etch, place is patterned to channel layer 805
Reason；The Mo source electrode and drain electrodes 806 of 50nm thickness are prepared using magnetron sputtering technique；The Si of 150nm thickness is prepared using PECVD3N4
Passivation layer 807.
Device is tested using method same as Example 2, obtains similar as a result, there is performance after annealing
It is substantially improved.
Embodiment 8
The present embodiment is prepared for a kind of device architecture of the thin film diode using metal substrate, and device architecture belongs to field
The structure of effect diode.
Figure 11 is the structure top view and sectional view of the thin film diode 900 manufactured in the present embodiment using metal substrate.
As shown in figure 11, thin film diode 900 includes Ni metal substrate 901, Si successively from top to bottom3N4Buffer protection layer 902, Cr
One electrode 903, Al2O3Insulating layer 904, IGZO channel layers 905, Au connection electrodes 906, Au second electrodes 907, SiO2Passivation layer
908。
The preparation method of the thin film diode is as follows：
The Cu that 5 μ m-thicks are electroplated on the Ni metal with rough surface of 20 μ m-thicks obtains the Ni metal substrate of 25 μ m-thicks
901, anode is Ni metal, and electroplate liquid is copper-bath, electric current 0.25A, voltage 2V.
The Si of 500nm thickness is prepared using PECVD on the Ni metal substrate 901 of 25 μ m-thicks3N4Buffer protection layer 902；Using
Magnetron sputtering technique prepares the Cr first electrodes 903 of 80nm thickness；The Al of 70nm thickness is prepared using ALD2O3Insulating layer 904；Using magnetic
Control sputtering technology prepares the IGZO channel layers 905 of 30nm thickness；The Au connection electrodes 906 of 100nm thickness are prepared using thermal evaporation techniques
With second electrode 907；The SiO of 100nm thickness is prepared using PECVD2Passivation layer 908.
It sets second electrode voltage to 0V, is scanned from -20V to 20V to first electrode voltage, obtains diode
Rectification characteristic curve.Similarly, performance has and is substantially improved after annealing.
Claims (10)
1. a kind of flexible metal substrate for making flexible thin-film transistor or thin film diode, the flexible metal substrate include
Metal foil and the coat of metal being attached on the metal foil surface, wherein by atomic force microscope at 10 × 10 μm
Scanning range under when observing, the r.m.s. roughness of the flexible metal substrate<10nm.
2. flexible metal substrate according to claim 1, wherein the r.m.s. roughness of the flexible metal substrate is
0.5~9.9nm, it is preferable that the thickness of the metal foil is 5~125 μm, and the thickness of the coat of metal is 1~25 μm.
3. flexible metal substrate according to claim 1 or 2, wherein the metal foil be Ag, Al, Au, Co, Cr,
It is one or more in Cu, Fe, Ir, Mo, Ni, Pb, Pd, Pt, Rh, Ru, Sn, Ta, Ti, V, W, Zr and stainless steel, the plating
Metal layer is one or more in Ag, Au, Cd, Co, Cr, Cu, Ir, Ni, Pb, Pd, Pt, Rh, W and Zn.
4. the preparation method of any one of claims 1 to 3 flexible metal substrate, the preparation method include：Using plating
Method forms the coat of metal in metal foil.
5. preparation method according to claim 4, wherein the galvanoplastic include：Metal foil is positioned over electroplating bath
In cathode site, anode is metal material to be plated, and electroplate liquid is added in electroplating bath；Apply electricity between cathode and anode
Stream and voltage, current range are 0.1~1A, and voltage range is 1~10V；It is taken out after obtaining required thickness, cleans and dry up.
6. a kind of flexible thin-film transistor, the flexible thin-film transistor include：Flexible metal substrate, buffer protection layer, raceway groove
Layer, gate insulation layer, gate electrode, source electrode, drain electrode and passivation layer, wherein the flexible metal substrate is claims 1 to 3
Any one of described in flexible metal substrate or claim 4 or 5 the methods made from flexible metal substrate.
7. flexible thin-film transistor according to claim 6, wherein the material of the buffer protection layer is aluminium oxide, oxygen
Change one or more in hafnium, silica, silicon nitride, titanium oxide, yttrium oxide, polyimides and polytetrafluoroethylene (PTFE)；Preferably, institute
The material for stating buffer protection layer is the mixture of polyimides and polytetrafluoroethylene (PTFE)；Preferably, the thickness of the buffer protection layer
It is 100nm to 1 μm.
8. a kind of fexible film diode, the fexible film diode include：Flexible metal substrate, buffer protection layer, raceway groove
Layer, insulating layer, first electrode, second electrode, connection electrode and passivation layer, wherein the flexible metal substrate is claim 1
To described in any one of 3 flexible metal substrate or claim 4 or 5 the methods made from flexible metal substrate.
9. fexible film diode according to claim 7, wherein the material of the buffer protection layer is aluminium oxide, oxygen
Change one or more in hafnium, silica, silicon nitride, titanium oxide, yttrium oxide, polyimides and polytetrafluoroethylene (PTFE)；Preferably, institute
The material for stating buffer protection layer is the mixture of polyimides and polytetrafluoroethylene (PTFE)；Preferably, the thickness of the buffer protection layer
It is 100nm to 1 μm.
10. a kind of method making flexible thin-film transistor or fexible film diode, the described method comprises the following steps：Using
Galvanoplastic form the coat of metal to prepare flexible metal substrate in metal foil；Buffering is deposited in the flexible metal substrate
Protective layer；Thin film transistor (TFT) or thin film diode are prepared on the buffer protection layer to form the flexible thin based on metal substrate
Film transistor or fexible film diode.
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| CN102534695A (en) * | 2010-12-29 | 2012-07-04 | 京东方科技集团股份有限公司 | Metal substrate for flexible display and preparation method for metal substrate |
| CN103299448A (en) * | 2010-09-29 | 2013-09-11 | Posco公司 | Method for manufacturing a flexible electronic device using a roll-shaped motherboard, flexible electronic device, and flexible substrate |
| CN104109888A (en) * | 2013-04-18 | 2014-10-22 | 株式会社Sh铜业 | Rolled copper foil with copper plated layer |
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| CN103299448A (en) * | 2010-09-29 | 2013-09-11 | Posco公司 | Method for manufacturing a flexible electronic device using a roll-shaped motherboard, flexible electronic device, and flexible substrate |
| CN102534695A (en) * | 2010-12-29 | 2012-07-04 | 京东方科技集团股份有限公司 | Metal substrate for flexible display and preparation method for metal substrate |
| CN102285166A (en) * | 2011-07-08 | 2011-12-21 | 昆山维信诺显示技术有限公司 | Base plate for flexible display device and method for manufacturing same |
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