CN107331710A - A kind of commutation diode thin-film device and preparation method thereof - Google Patents
A kind of commutation diode thin-film device and preparation method thereof Download PDFInfo
- Publication number
- CN107331710A CN107331710A CN201710522800.3A CN201710522800A CN107331710A CN 107331710 A CN107331710 A CN 107331710A CN 201710522800 A CN201710522800 A CN 201710522800A CN 107331710 A CN107331710 A CN 107331710A
- Authority
- CN
- China
- Prior art keywords
- film
- substrate
- thin
- film device
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010408 film Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims description 54
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910003865 HfCl4 Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910006227 ZrO4 Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000000224 chemical solution deposition Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- 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
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- 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
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- 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
Landscapes
- 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)
- Electrodes Of Semiconductors (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The present invention provides a kind of commutation diode thin-film device, including substrate, the sull being compounded in substrate, the hearth electrode being arranged in substrate and the top electrode being arranged on the sull；The sull is Hf0.5Zr0.5O2Film.Hf in the present invention0.5Zr0.5O2Thin-film device has obvious diode effect, and has good compatibility with CMOS technology, is conducive to carrying out Large scale processes production.Present invention also offers a kind of commutation diode thin-film device, the present invention prepares Hf using chemical solution deposition0.5Zr0.5O2For film, and other relative diode preparation methods, the film composition in the present invention is easily controlled, and preparation method is simple, and the thin-film device rectification characteristic prepared is obvious.
Description
Technical field
The invention belongs to technical field of semiconductors, more particularly to a kind of commutation diode thin-film device and preparation method thereof.
Background technology
Commutation diode belongs to semi-conducting material, with unilateral conduction, can be direct current by AC conversion, extensive
Applied to every field, such as automotive field, solar energy industry, domestic electronic field etc., it may be said that the electricity of nearly all charged
Subassembly all uses commutation diode, and indispensable status is occupied in field of semiconductor devices.
But, the prevailing technology CMOS technology of conventional commutation diode and current integrated circuit is incompatible at present, such as mesh
Preceding conventional Schottky diode, it is incompatible with CMOS technology, it is impossible to other cmos circuit single-chip integrations, to integrated circuit
Large-scale production brings very big puzzlement.
The content of the invention
It is an object of the invention to provide a kind of commutation diode thin-film device and preparation method thereof, the rectification in the present invention
Diode thin-film device can be good at compatible with CMOS technology.
The present invention provides a kind of commutation diode thin-film device, including substrate, be compounded in substrate sull, set
Put the hearth electrode in substrate and the top electrode being arranged on the sull；
The sull is Hf0.5Zr0.5O2Film.
It is preferred that, the substrate is selected from Si, ITO electro-conductive glass, FTO electro-conductive glass, GaAs, Pt/Ti/SiO2/Si、
SrTiO3:One or more in Nb and ITO/PET.
It is preferred that, the top electrode is the one or more in Pt, Au, Ag, W, Al, Ti, TiN.
It is preferred that, the hearth electrode is the one or more in Pt, Au, Ag, W, Al, Ti, TiN.
The present invention provides a kind of preparation method of commutation diode thin-film device, comprises the following steps：
A) by Hf0.5Zr0.5O2Precursor liquid, which is coated in after substrate surface, drying, to be obtained being coated with Hf0.5Zr0.5O2The base of precursor film
Bottom；
B Hf will) be coated with0.5Zr0.5O2The substrate of precursor film is annealed 10~20min at 450~500 DEG C, obtains plating aerobic
The substrate of compound film；
C top electrode) is plated on the sull surface, hearth electrode is plated on the substrate, obtains imitating with diode
The thin-film device answered.
It is preferred that, the Hf0.5Zr0.5O2Precursor liquid is made according to following steps：
By HfCl4It is dissolved in absolute ethyl alcohol, is stirred at 30~50 DEG C while watery hydrochloric acid is added, until being completely dissolved in second
Alcohol, continues to stir 2~5 hours afterwards, obtains HfO2Precursor liquid；
By ZrO4C16H36It is dissolved in acetylacetone,2,4-pentanedione, 30~50 DEG C of stirrings are dissolved for 2~5 hours to abundant, obtain ZrO2Forerunner
Liquid；
By HfO2Precursor liquid is added dropwise to ZrO2In precursor liquid, stir 2~5 hours, adjusted with acetylacetone,2,4-pentanedione at 50~70 DEG C
The concentration of solution is 0.1~0.3mol/L, obtains Hf0.5Zr0.5O2Precursor liquid.
It is preferred that, it is described to be applied to rotary coating, be specially：
First with 500~1000r/min rotating speed 15~30s of spin coating, then 15 are rotated with 2000~3000r/min rotating speed
~20s.
It is preferred that, the drying comprises the following steps：
10~30min is first dried at 180 DEG C, then with 300 DEG C of 30~60min of drying, is coated with
Hf0.5Zr0.5O2The substrate of precursor film.
It is preferred that, the atmosphere of the annealing is air atmosphere, oxygen atmosphere or nitrogen atmosphere.
It is preferred that, the step A) and B) between it is further comprising the steps of：
Using the hydrofluoric acid of alkene by Hf0.5Zr0.5O2Precursor film wipes one jiao, exposed portion substrate.
The present invention provides a kind of commutation diode thin-film device, including substrate, be compounded in substrate sull, set
Put the hearth electrode in substrate and the top electrode being arranged on the sull；The sull is Hf0.5Zr0.5O2
Film.Hf in the present invention0.5Zr0.5O2Thin-film device has obvious diode effect, and has well with CMOS technology
Compatibility, be conducive to carry out Large scale processes production.
Present invention also offers a kind of commutation diode thin-film device, the present invention is prepared using chemical solution deposition
Hf0.5Zr0.5O2For film, and other relative diode preparation methods, the film composition in the present invention is easily controlled, preparation side
Method is simple, and the thin-film device rectification characteristic prepared is obvious.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the structure of thin film device schematic diagram in the embodiment of the present invention 1 in acquisition；
Fig. 2 is the I-V diagram of thin-film device in the embodiment of the present invention 1；
Fig. 3 is the I-V diagram of thin-film device in the embodiment of the present invention 4.
Embodiment
The invention provides a kind of commutation diode thin-film device, including substrate, be compounded in substrate sull,
The hearth electrode being arranged in substrate and the top electrode being arranged on the sull；
The sull is Hf0.5Zr0.5O2Film.
In the present invention, the substrate is preferably selected from Si, ITO electro-conductive glass, FTO electro-conductive glass, GaAs, Pt/Ti/
SiO2/Si、SrTiO3:One or more in Nb and ITO/PET；The top electrode is preferably Pt, Au, Ag, W, Al, Ti, TiN
In one or more；The hearth electrode is preferably the one or more in Pt, Au, Ag, W, Al, Ti, TiN.It is right in the present invention
The thickness and size of the substrate, top electrode and hearth electrode do not have special limitation, and the size of the sull is preferably small
Size in base, hearth electrode is set to reserve enough positions in substrate.
Present invention also offers a kind of preparation method of commutation diode thin-film device, comprise the following steps：
A) by Hf0.5Zr0.5O2Precursor liquid, which is coated in after substrate surface, drying, to be obtained being coated with Hf0.5Zr0.5O2The base of precursor film
Bottom；
B Hf will) be coated with0.5Zr0.5O2The substrate of precursor film is annealed 10~20min at 450~500 DEG C, obtains plating aerobic
The substrate of compound film；
C top electrode) is plated on the sull surface, hearth electrode is plated on the substrate, obtains imitating with diode
The thin-film device answered.
First, the present invention prepares Hf according to following steps0.5Zr0.5O2Precursor liquid：
The present invention is with hafnium chloride HfCl4(99.5%) as raw material；Absolute ethyl alcohol is used as solvent.It is according to chemistry meter first
Ratio is measured by hafnium chloride HfCl4(99.5%) it is dissolved in absolute ethyl alcohol, stirs while add watery hydrochloric acid, prevent at 30~50 DEG C
HfCl4Hydrolysis, untill ethanol is completely dissolved in, continues to stir 2~5 hours afterwards, ultimately forms HfO2Precursor liquid.
Use zirconium-n-butylate ZrO4C16H36(80%) as raw material；Acetylacetone,2,4-pentanedione is used as solvent.Will just according to stoichiometric proportion
Butanol zirconium ZrO4C16H36(80%) it is dissolved in acetylacetone,2,4-pentanedione, 30~50 DEG C of stirrings are dissolved for 2~5 hours to abundant, are ultimately formed
ZrO2Precursor liquid.
By HfO2Precursor liquid is added dropwise to ZrO2In precursor liquid, stir 2~5 hours, adjusted with acetylacetone,2,4-pentanedione at 50~70 DEG C
The concentration of solution is 0.1~0.3mol/L, obtains Hf0.5Zr0.5O2(HZO) precursor liquid.
Obtain Hf0.5Zr0.5O2After precursor liquid, the present invention uses spin coating proceeding by Hf0.5Zr0.5O2Precursor liquid is coated in substrate
Obtain being coated with Hf after surface, drying0.5Zr0.5O2The substrate of precursor film.
Wipe surface to remove the SiO on Si pieces surface present invention preferably employs dilute hydrofluoric acid2, then will be described
Hf0.5Zr0.5O2Precursor liquid is added drop-wise to dropwise to be realized in cleaned substrate, is then placed on sol evenning machine and is carried out spin coating, first
With 500~1000r/min rotating speed low speed 15~30s of spin coating, then 15 are kept with 2000~3000r/min rotating speed again~
20s, completes coating.
Then coated wet film is placed on warm table and dried, the process of the drying is specially：First at 180 DEG C
10~30min is to remove the moisture in based Dehumidification Membranes for lower drying, then with 300 DEG C of progress 30~60min of roasting glue, makes organic in film
Thing is decomposed, and obtains being coated with Hf0.5Zr0.5O2The substrate of precursor film.
The present invention is preferably coated with 2~3 Hf0.5Zr0.5O2Precursor liquid, with the precursor film of thickness needed for obtaining, often coats one
Layer, just according to the drying of above-mentioned stoving process once, until the precursor film of thickness needed for obtaining.
Hf is wiped present invention preferably employs the hydrofluoric acid of alkene0.5Zr0.5O2One jiao of precursor film, so that exposed portion substrate is come
Plate hearth electrode.
Hf is coated with described in obtaining0.5Zr0.5O2After the substrate of precursor film, the present invention is moved back it in quick anneal oven
Fire, obtains being coated with the substrate of sull.The temperature of the annealing is 450~500 DEG C；The time of the annealing be 10~
20min；The atmosphere of the annealing is preferably air atmosphere, oxygen atmosphere or nitrogen atmosphere.
Complete after annealing, present invention preferably employs template encapsulation method, the surface for obtained sull of annealing is sputtered
One layer of a diameter of 0.5mm top electrode, hearth electrode, the material of the hearth electrode and top electrode are plated on the conductive film surface exposed
Matter is consistent with the material of above hearth electrode and top electrode, will not be repeated here.
The present invention provides a kind of commutation diode thin-film device, including substrate, be compounded in substrate sull, set
Put the hearth electrode in substrate and the top electrode being arranged on the sull；The sull is Hf0.5Zr0.5O2
Film.Hf in the present invention0.5Zr0.5O2Thin-film device has obvious diode effect, and has well with CMOS technology
Compatibility, be conducive to carry out Large scale processes production.
Present invention also offers a kind of commutation diode thin-film device, the present invention is prepared using chemical solution deposition
Hf0.5Zr0.5O2For film, and other relative diode preparation methods, the film composition in the present invention is easily controlled, preparation side
Method is simple, and the thin-film device rectification characteristic prepared is obvious.
In order to further illustrate the present invention, a kind of commutation diode film device provided with reference to embodiments the present invention
Part and preparation method thereof is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
Hf is prepared using chemical solution deposition0.5Zr0.5O2(HZO) sull device：
With hafnium chloride HfCl4(99.5%) as raw material；Absolute ethyl alcohol is used as solvent.Being first will according to stoichiometric proportion
Hafnium chloride HfCl4(99.5%) it is dissolved in absolute ethyl alcohol, is stirred at 30 DEG C while add watery hydrochloric acid, prevent HfCl4Hydrolysis,
Untill ethanol is completely dissolved in, continues to stir 2 hours afterwards, ultimately form HfO2Precursor liquid.
Use zirconium-n-butylate ZrO4C16H36(80%) as raw material；Acetylacetone,2,4-pentanedione is used as solvent.Will just according to stoichiometric proportion
Butanol zirconium ZrO4C16H36(80%) it is dissolved in acetylacetone,2,4-pentanedione, 30 DEG C of stirrings are dissolved for 2 hours to abundant, ultimately form ZrO2Forerunner
Liquid.
By HfO2Precursor liquid is added dropwise to ZrO2In precursor liquid, stirred 2 hours at 70 DEG C, solution is adjusted with acetylacetone,2,4-pentanedione
Concentration is 0.3mol/L, obtains Hf0.5Zr0.5O2(HZO) precursor liquid.
By Hf0.5Zr0.5O2(HZO) precursor liquid is spun and coated on silicon chip, the low speed 800r/min on sol evenning machine, spin coating
30s, subsequent 3000r/min rotations keep 20s, often coat one layer, and wet film is dried 30min to remove on warm table at 180 DEG C
Moisture in film, 300 DEG C of roasting glue 60min are so repeated 2 times, the forerunner of thickness needed for obtaining so that organic matter in film is decomposed
Film.Then one jiao that precursor film is wiped with the hydrofluoric acid of alkene, exposes a part of silicon chip, and it is finally used into air at 500 DEG C
Atmosphere annealing 20min.Obtain sull.
One layer of diameter 0.5mm gold is sputtered on sull using template encapsulation method as top electrode, exposed
The angle surface of silicon chip one is gold-plated as hearth electrode, obtains commutation diode thin-film device.
Obtained structure of thin film device is as shown in figure 1, Fig. 1 is the structure of thin film device in the embodiment of the present invention 1 in acquisition
Schematic diagram.This thin-film device makes simple and convenient as can see from Figure 1, and HZO films only need to be plated to obtain on Si pieces, are easy to
Large-scale production.
The thin-film device that the present invention is obtained to the present embodiment carries out I-V tests, as a result as shown in Fig. 2 Fig. 2 is real for the present invention
The I-V diagram of thin-film device in example 1 is applied, as seen from Figure 2, the thin-film device unilateal conduction in the present embodiment, with diode
Effect, rectification characteristic is notable.
Embodiment 2~3
Thin-film device is prepared according to the preparation method in embodiment 1, unlike, respectively using oxygen and nitrogen to move back
Internal heat atmosphere.
The present invention has equally also carried out I-V tests to the thin-film device that embodiment 2 and embodiment 3 are obtained, and is respectively provided with two poles
Tube effect, rectification characteristic is notable.
Embodiment 4
Prepared according to the method in embodiment 1 and obtain HfO2And ZrO2Precursor liquid；
Two hours are stirred in the environment of 50 DEG C, the concentration that solution is adjusted with acetylacetone,2,4-pentanedione is 0.2mol/L, is obtained into
Hf0.5Zr0.5O2(HZO) precursor liquid.
By Hf0.5Zr0.5O2(HZO) precursor liquid is spun and coated on FTO electro-conductive glass, the low speed 500r/ on sol evenning machine
Min, spin coating 15s, subsequent 2000r/min rotations keep 15s, often coat one layer, and wet film is dried into 10min 180 DEG C on warm table
So that organic matter in film is decomposed, to be so repeated 3 times except the moisture in striping, 300 DEG C of roasting glue 30min, obtain required thickness
Precursor film.Then one jiao that precursor film is wiped with the hydrofluoric acid of alkene, exposes a part of FTO electro-conductive glass, finally at 450 DEG C
Using air atmosphere annealing 10min.Obtain sull.
One layer of diameter 0.5mm gold is sputtered on sull using template encapsulation method as top electrode, exposed
The angle surface of silicon chip one is gold-plated as hearth electrode, obtains commutation diode thin-film device.
The thin-film device that the present invention is obtained to the present embodiment carries out I-V tests, as a result as shown in figure 3, Fig. 3 is real for the present invention
Apply the I-V diagram of thin-film device in example 4.As seen from Figure 3, the thin-film device unilateal conduction in the present embodiment, with diode
Effect, rectification characteristic is notable.
Embodiment 5~6
Thin-film device is prepared according to the preparation method in embodiment 4, unlike, respectively using oxygen and nitrogen to move back
Internal heat atmosphere.
The present invention has equally also carried out I-V tests to the thin-film device that embodiment 5 and embodiment 6 are obtained, and is respectively provided with two poles
Tube effect, rectification characteristic is notable.
Embodiment 7~9
Method according to embodiment 4, which is prepared, obtains Hf0.5Zr0.5O2(HZO) precursor liquid；
By Hf0.5Zr0.5O2(HZO) precursor liquid is spun and coated on ITO electro-conductive glass, the low speed 500r/ on sol evenning machine
Min, spin coating 15s, subsequent 2000r/min rotations keep 15s, often coat one layer, and wet film is dried into 10min 180 DEG C on warm table
So that organic matter in film is decomposed, to be so repeated 3 times except the moisture in striping, 300 DEG C of roasting glue 30min, obtain required thickness
Precursor film.Then one jiao that precursor film is wiped with the hydrofluoric acid of alkene, exposes a part of ITO electro-conductive glass, finally at 450 DEG C
Air atmosphere, oxygen atmosphere and nitrogen atmosphere annealing 10min is respectively adopted, sull is obtained.
The present invention has equally also carried out I-V tests to the thin-film device that embodiment 7~9 is obtained, what embodiment 7~9 was obtained
Thin-film device is respectively provided with diode effect, and rectification characteristic is notable.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of commutation diode thin-film device, including substrate, be compounded in substrate sull, be arranged in substrate
Hearth electrode and the top electrode being arranged on the sull；
The sull is Hf0.5Zr0.5O2Film.
2. commutation diode thin-film device according to claim 1, it is characterised in that it is conductive that the substrate is selected from Si, ITO
Glass, FTO electro-conductive glass, GaAs, Pt/Ti/SiO2/Si、SrTiO3:One or more in Nb and ITO/PET.
3. commutation diode thin-film device according to claim 1, it is characterised in that the top electrode be Pt, Au, Ag,
One or more in W, Al, Ti, TiN.
4. commutation diode thin-film device according to claim 1, it is characterised in that the hearth electrode be Pt, Au, Ag,
One or more in W, Al, Ti, TiN.
5. a kind of preparation method of commutation diode thin-film device, comprises the following steps：
A) by Hf0.5Zr0.5O2Precursor liquid, which is coated in after substrate surface, drying, to be obtained being coated with Hf0.5Zr0.5O2The substrate of precursor film；
B Hf will) be coated with0.5Zr0.5O2The substrate of precursor film is annealed 10~20min at 450~500 DEG C, obtains being coated with oxide thin
The substrate of film；
C top electrode) is plated on the sull surface, hearth electrode is plated on the substrate, is obtained with diode effect
Thin-film device.
6. preparation method according to claim 5, it is characterised in that the Hf0.5Zr0.5O2Precursor liquid is according to following steps
It is made：
By HfCl4It is dissolved in absolute ethyl alcohol, is stirred at 30~50 DEG C while add watery hydrochloric acid, until ethanol is completely dissolved in, it
Continue to stir 2~5 hours afterwards, obtain HfO2Precursor liquid；
By ZrO4C16H36It is dissolved in acetylacetone,2,4-pentanedione, 30~50 DEG C of stirrings are dissolved for 2~5 hours to abundant, obtain ZrO2Precursor liquid；
By HfO2Precursor liquid is added dropwise to ZrO2In precursor liquid, stirred 2~5 hours at 50~70 DEG C, solution is adjusted with acetylacetone,2,4-pentanedione
Concentration be 0.1~0.3mol/L, obtain Hf0.5Zr0.5O2Precursor liquid.
7. preparation method according to claim 5, it is characterised in that described to be applied to rotary coating, is specially：
First with 500~1000r/min rotating speed 15~30s of spin coating, then with 2000~3000r/min rotating speed rotation 15~
20s。
8. preparation method according to claim 5, it is characterised in that the drying comprises the following steps：
10~30min is first dried at 180 DEG C, then with 300 DEG C of 30~60min of drying, obtains being coated with Hf0.5Zr0.5O2Forerunner
The substrate of film.
9. preparation method according to claim 5, it is characterised in that the atmosphere of the annealing is air atmosphere, oxygen gas
Atmosphere or nitrogen atmosphere.
10. preparation method according to claim 5, it is characterised in that the step A) and B) between also include following step
Suddenly：
Using the hydrofluoric acid of alkene by Hf0.5Zr0.5O2Precursor film wipes one jiao, exposed portion substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710522800.3A CN107331710A (en) | 2017-06-30 | 2017-06-30 | A kind of commutation diode thin-film device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710522800.3A CN107331710A (en) | 2017-06-30 | 2017-06-30 | A kind of commutation diode thin-film device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107331710A true CN107331710A (en) | 2017-11-07 |
Family
ID=60198606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710522800.3A Pending CN107331710A (en) | 2017-06-30 | 2017-06-30 | A kind of commutation diode thin-film device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107331710A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190134A (en) * | 2019-06-14 | 2019-08-30 | 广东工业大学 | A kind of amorphous oxide thin film device and preparation method thereof |
| CN110534434A (en) * | 2019-07-15 | 2019-12-03 | 华南理工大学 | A kind of method that solwution method prepares metal oxide TFD |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101577311A (en) * | 2009-06-09 | 2009-11-11 | 中国科学院微电子研究所 | One-time programming memory and manufacturing method thereof |
-
2017
- 2017-06-30 CN CN201710522800.3A patent/CN107331710A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101577311A (en) * | 2009-06-09 | 2009-11-11 | 中国科学院微电子研究所 | One-time programming memory and manufacturing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A.CHOUPRIK 等: "Electron transport across ultrathin ferroelectric Hf0.5Zr0.5O2 films on Si", 《MICROELECTRONIC ENGINEERING》 * |
| JUN YOUNG LEE等: "Structural properties of solution-processed Hf0.5Zr0.5O2 thin film", 《CURRENT APPLIED PHYSICS》 * |
| M.H.LEE等: "Steep Slope and Near Non-Hysteresis of FETs With Antiferroelectric-Like HfZrO for Low-Power Electronics", 《IEEE ELECTRON DEVICE LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190134A (en) * | 2019-06-14 | 2019-08-30 | 广东工业大学 | A kind of amorphous oxide thin film device and preparation method thereof |
| CN110190134B (en) * | 2019-06-14 | 2022-06-24 | 广东工业大学 | Amorphous oxide thin film device and preparation method thereof |
| CN110534434A (en) * | 2019-07-15 | 2019-12-03 | 华南理工大学 | A kind of method that solwution method prepares metal oxide TFD |
| CN110534434B (en) * | 2019-07-15 | 2021-11-19 | 华南理工大学 | Method for preparing metal oxide TFD (thin film transistor) by solution method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004048A (en) | A kind of preparation method of the inorganic perovskite quantum dot film of caesium lead bromine and photovoltaic device based on it | |
| CN109037398B (en) | Preparation method of cesium tin iodine film and photovoltaic device based on cesium tin iodine film | |
| WO2018028244A1 (en) | Transparent conductive film, preparation method therefor and application thereof | |
| CN105449104A (en) | Perovskite solar cell with stable performance in air environment and preparation method of perovskite solar cell | |
| CN100587910C (en) | Preparation for ferroelectric material with quartz/lanthanum nickelate/bismuth ferrite-lead titanate three-layer structure | |
| CN108796532A (en) | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis | |
| CN108321299B (en) | Low-dimensional lead-free perovskite thin film and preparation method of lead-free perovskite solar cell | |
| CN103360107B (en) | A kind of gold-nickel acid lanthanum composite conductive thin film material and preparation method thereof | |
| CN106784332A (en) | A kind of PEDOT:PSS‑MoO3The preparation method of/silicon nanowire array organic inorganic hybridization solar cell | |
| CN107394043A (en) | A kind of flexible optoelectronic conversion equipment and preparation method thereof | |
| CN107331710A (en) | A kind of commutation diode thin-film device and preparation method thereof | |
| CN108232017A (en) | A kind of perovskite solar cell of efficient cryogenic and preparation method thereof | |
| CN108281550B (en) | Based on the titania-doped perovskite solar battery and preparation method thereof of magnesium | |
| CN103107242B (en) | Prepare the method for pucherite solar cell on the glass substrate | |
| CN111710786A (en) | Flexible electron transport layer film forming process | |
| CN108832007A (en) | A kind of preparation method of perovskite and semi-conductor type silicon hybrid solar cell | |
| CN104810478A (en) | Solar cell with tin perovskite structure and manufacturing method thereof | |
| CN208444862U (en) | A kind of resistance-variable storing device based on perovskite material | |
| CN108123045A (en) | A kind of unleaded perovskite solar cell and preparation method thereof | |
| CN115605063A (en) | Method for preparing high-performance perovskite film from ordered porous lead iodide and application | |
| CN109638168A (en) | It is a kind of to prepare efficient perovskite solar battery and preparation method using green mixing anti-solvent | |
| CN105679856A (en) | Preparation method for Mg-doped ZnO thin film window layer through low-temperature solution method and application therefor | |
| CN104638110B (en) | A kind of perovskite solar cell based on meso-hole structure indium sulphur and preparation method thereof | |
| CN106887521A (en) | A kind of flexible translucent perovskite solar cell | |
| CN103708848B (en) | Preparation method of composite structure high electric energy density thick film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ge Pengzu Inventor after: Tang Xingui Inventor after: Mo Zhiye Inventor after: Liu Qiuxiang Inventor after: Jiang Yanping Inventor before: Tang Xingui Inventor before: Mo Zhiye Inventor before: Liu Qiuxiang Inventor before: Jiang Yanping |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171107 |