CN110061108B - Preparation method of high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode - Google Patents
Preparation method of high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode Download PDFInfo
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- CN110061108B CN110061108B CN201910388716.6A CN201910388716A CN110061108B CN 110061108 B CN110061108 B CN 110061108B CN 201910388716 A CN201910388716 A CN 201910388716A CN 110061108 B CN110061108 B CN 110061108B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NBNNNTZKPYWYBN-UHFFFAOYSA-N [Si+4].[S-2].[Cd+2].[S-2].[S-2] Chemical compound [Si+4].[S-2].[Cd+2].[S-2].[S-2] NBNNNTZKPYWYBN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 60
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 63
- 229910052710 silicon Inorganic materials 0.000 claims description 63
- 239000010703 silicon Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 12
- 239000002120 nanofilm Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 10
- 238000005401 electroluminescence Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table
- H01L33/285—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table characterised by the doping materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/34—Materials of the light emitting region containing only elements of Group IV of the Periodic Table
- H01L33/346—Materials of the light emitting region containing only elements of Group IV of the Periodic Table containing porous silicon
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Abstract
The invention relates to the technical field of semiconductor light-emitting devices, and discloses a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode, which comprises the following steps: firstly, acetone or ethanol and a standard RCA cleaning process are sequentially adopted to carry out primary cleaning and deep cleaning on the P-type heavily-doped monocrystalline silicon wafer. Then, preparing the nano porous silicon columnar array by adopting a hydrothermal corrosion method. And finally, preparing the aluminum-doped cadmium sulfide nano film and the nano porous silicon columnar array by using a chemical water bath method by using the nano porous silicon columnar array as a substrate and aluminum chloride as a dopant. The novel light-emitting diode constructed by organically combining the aluminum-doped cadmium sulfide nano-film and the nano-porous silicon columnar array can fully utilize the array and the porous structure of the nano-porous silicon columnar array, and simultaneously can effectively increase the carrier recombination efficiency and improve the light-emitting efficiency of the light-emitting diode by utilizing the higher carrier mobility of the doped cadmium sulfide and the nano-porous silicon columnar array.
Description
Technical Field
The invention relates to the technical field of semiconductor light-emitting devices, in particular to a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode.
Background
Cadmium sulfide is a wide band gap compound semiconductor with a direct band gap, has the characteristics of high thermal conductivity, high electron mobility, good chemical stability and the like, is known as an ideal luminescent material, and is widely applied to manufacturing yellow-green light emitting diodes. Silicon is a core material of modern electronic devices, and has the advantages of mature preparation process, easy realization of device integration and the like. However, due to the difference of lattice constant, lattice structure and thermal expansion coefficient between cadmium sulfide and silicon, serious problems of lattice mismatch, internal stress and the like are caused, so that it is difficult to directly grow cadmium sulfide on a silicon substrate to prepare a silicon-based cadmium sulfide light-emitting device. Cadmium sulfide itself generates a large number of defects during growth, and thus constitutes a defect level luminescence center, and a wide emission band appears in the photoluminescence spectrum thereof. Therefore, in most cases, the prepared cadmium sulfide heterostructure electroluminescent device has low luminous efficiency and large emission bandwidth due to the existence of a large number of defects, and is difficult to form a high-efficiency stable heterostructure.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode, which has the advantages of low energy consumption, high luminous efficiency and the like and solves the problems of high energy consumption and low luminous efficiency of the conventional diode.
(II) technical scheme
In order to achieve the purposes of low energy consumption and high luminous efficiency, the invention provides the following technical scheme: a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode comprises the following steps:
step A, placing the cut P-type heavily-doped monocrystalline silicon piece into an acetone or ethanol solution for soaking to remove surface organic pollutants, and then carrying out deep cleaning on the silicon piece by using a standard RCA cleaning process;
b, fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid into the reaction kettle;
step C, putting the reaction kettle into a drying box, and performing heating treatment and heat preservation treatment;
d, taking out the silicon wafer from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array;
step E, adding 0.03mol/L of cadmium acetate and 0.0018mol/L ([ Al ]]/[Cd]0.06) AlCl3·6H2Dissolving O in 75ml deionized water to obtain solution A, and adding 0Dissolving 1mol/L thiourea in 10ml deionized water to prepare solution B;
step F, adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath;
step G, vertically placing the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature;
step H, after the reaction in step G is finished, taking out the sample, repeatedly washing the sample with deionized water, and drying the washed silicon wafer in a drying box to finally prepare the aluminum-doped cadmium sulfide/nano-silicon heterostructure array with the doping concentration [ Al ]/[ Cd ] of 0.06(0.06 is the molar concentration ratio of Al ions to Cd ions);
step I, sequentially adopting dilute HCl and hot saturated NaOH solution to remove a yellow cadmium sulfide film and a nano porous silicon columnar array on the surface of one side of a sample until the surface becomes silver gray, exposing a single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid to obtain an aluminum-doped cadmium sulfide/silicon nano heterostructure array;
and step J, depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of the cadmium sulfide and the monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, and obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
Preferably, the P-type heavily doped monocrystalline silicon piece cut in the step A is soaked in an acetone or ethanol solution for 5 minutes.
Preferably, the etching solution in the step B consists of 0.03mol/L ferric nitrate nonahydrate, 13mol/L hydrofluoric acid and deionized water, and the filling degree of the reaction kettle is 83%.
Preferably, the temperature of the temperature raising treatment in the step C is 142 ℃, and the holding time is 45 minutes.
Preferably, the constant temperature heating time in the step G is 40 minutes.
Preferably, in the step H, the temperature in the drying oven is 80 ℃, and the drying time is 20 minutes.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode, which has the following beneficial effects:
1. the invention aims to provide a novel semiconductor nano-film silicon-based heterojunction light-emitting diode with good luminous efficiency in a visible light wave band, and the novel heterostructure array light-emitting diode is formed by compounding a P-type nano-porous silicon columnar array substrate and N-type aluminum-doped nano cadmium sulfide. The result shows that the proper amount of Al is doped to effectively improve the uniformity and compactness of the cadmium sulfide nano film, increase the carrier mobility and reduce the square resistivity of the film. The starting working voltage of the heterojunction light-emitting diode can be effectively reduced, the rectification characteristic of the light-emitting diode is obviously improved, the electroluminescent intensity of the light-emitting diode is obviously enhanced, and stable high-intensity electroluminescence with the full width at half maximum of 39nm can be realized at lower voltage.
2. The novel light-emitting diode constructed by organically combining the aluminum-doped cadmium sulfide nano-film and the nano-porous silicon columnar array can make full use of the array and the porous structure of the nano-porous silicon columnar array, and a large amount of nano-heterojunction can be formed after the combination of the array and the porous structure. Each heterojunction can be a carrier transmission channel, and simultaneously, the doped cadmium sulfide and the higher carrier mobility of the nano porous silicon columnar array are utilized, so that the carrier recombination efficiency can be effectively increased, and the light emitting efficiency of the light emitting diode is improved.
Description of the drawings:
FIG. 1 is a flow chart of the preparation of an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction light emitting diode according to the invention;
FIG. 2 is a scanning electron microscope image of a nanoporous silicon columnar array in accordance with the present invention;
FIG. 3 is a scanning electron microscope image of an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction according to the present invention;
FIG. 4 is a transmission electron microscope image of an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction according to the present invention;
FIG. 5 is a high resolution transmission electron microscope image of an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction of the present invention;
FIG. 6 is a graph of current density versus voltage for an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction light emitting diode in accordance with the present invention;
FIG. 7 is an electroluminescence image of a 0.06 concentration ratio Al-doped CdS/nanoporous Si columnar array heterojunction light emitting diode of the present invention;
FIG. 8 is an energy band diagram of an Al-doped CdS/nanoporous Si columnar array heterojunction LED according to the present invention;
FIG. 9 is a color coordinate diagram of an aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction light emitting diode of the present invention;
FIG. 10 is an electroluminescence image of an undoped aluminum-doped cadmium sulfide/nanoporous silicon columnar array heterojunction light emitting diode of the present invention;
FIG. 11 is an electroluminescence image of a heterojunction light emitting diode with a 0.02 concentration ratio of aluminum-doped cadmium sulfide/nanoporous silicon columnar array according to the present invention;
FIG. 12 electroluminescent diagram of a 0.1 concentration ratio Al-doped cadmium sulfide/nanoporous Si columnar array heterojunction light emitting diode of the present invention
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
(1) Preparation and post-treatment of P-type nano porous silicon columnar array
The process for preparing the P-type nano porous silicon columnar array by using the hydrothermal corrosion method comprises the following steps: (1) firstly, placing a cut P-type heavily-doped monocrystalline silicon wafer into an acetone or ethanol solution for soaking for 5min to remove surface organic pollutants, and then carrying out deep cleaning on the silicon wafer by using a standard RCA cleaning process. (2) Fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid (consisting of 0.03mol/L ferric nitrate nonahydrate, 13mol/L hydrofluoric acid and deionized water, wherein the filling degree of the reaction kettle is 83%) into the reaction kettle. (3) And (3) putting the reaction kettle into a drying box, heating to 142 ℃, preserving heat for 45 minutes, taking out the reaction kettle from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array.
(2) Preparation and post-treatment of growing aluminum-doped cadmium sulfide/silicon nano heterostructure array
And depositing the aluminum-doped cadmium sulfide nano film on the prepared P-type nano porous silicon columnar array serving as a substrate by utilizing a chemical water bath deposition technology.
0.03mol/L of cadmium acetate and 0.0018mol/L ([ Al)]/[Cd]0.06) AlCl3·6H2Dissolving O in 75ml of deionized water to prepare a solution A; dissolving 0.1mol/L thiourea in 10ml deionized water to prepare solution B; adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath; vertically putting the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature for 40 min; and after the reaction is finished, taking out the sample, repeatedly washing the sample by using deionized water, and drying the cleaned silicon wafer in a drying oven for 20 minutes at the temperature of 80 ℃. Finally the doping concentration [ Al ] is obtained]/[Cd]0.06(0.06 is the molar concentration ratio of Al ions to Cd ions) aluminum-doped cadmium sulfide/nano-silicon heterostructure array. By adopting a similar method, different concentrations of doped Al can be obtained by changing the amount of AlCl3 & 6H2O]/[Cd]The sample of (1).
And finally, sequentially removing the yellow cadmium sulfide film and the nano porous silicon columnar array on the surface of one side of the sample by using dilute HCl and hot saturated NaOH solution until the surface is changed into silver gray, exposing the single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid, thereby obtaining the aluminum-doped cadmium sulfide/silicon nano heterostructure array.
(3) Electrode preparation
And depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of cadmium sulfide and monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, thus obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
The first embodiment is as follows:
a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode comprises the following steps:
step A, placing the cut P-type heavily-doped monocrystalline silicon piece into an acetone or ethanol solution for soaking to remove surface organic pollutants, and then carrying out deep cleaning on the silicon piece by using a standard RCA cleaning process;
b, fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid into the reaction kettle;
step C, putting the reaction kettle into a drying box, and performing heating treatment and heat preservation treatment;
d, taking out the silicon wafer from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array;
e, dissolving 0.03mol/L cadmium acetate in 75ml deionized water to prepare a solution A, and dissolving 0.1mol/L thiourea in 10ml deionized water to prepare a solution B;
step F, adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath;
step G, vertically placing the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature;
step H, after the reaction in step G is finished, taking out the sample, repeatedly washing the sample with deionized water, and drying the washed silicon wafer in a drying box to finally prepare the aluminum-doped cadmium sulfide/nano-silicon heterostructure array with the doping concentration [ Al ]/[ Cd ] of 0.06(0.06 is the molar concentration ratio of Al ions to Cd ions);
step I, sequentially adopting dilute HCl and hot saturated NaOH solution to remove a yellow cadmium sulfide film and a nano porous silicon columnar array on the surface of one side of a sample until the surface becomes silver gray, exposing a single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid to obtain an aluminum-doped cadmium sulfide/silicon nano heterostructure array;
and step J, depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of the cadmium sulfide and the monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, and obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
The resulting electroluminescence pattern is shown in FIG. 10.
Example two:
a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode comprises the following steps:
step A, placing the cut P-type heavily-doped monocrystalline silicon piece into an acetone or ethanol solution for soaking to remove surface organic pollutants, and then carrying out deep cleaning on the silicon piece by using a standard RCA cleaning process;
b, fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid into the reaction kettle;
step C, putting the reaction kettle into a drying box, and performing heating treatment and heat preservation treatment;
d, taking out the silicon wafer from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array;
step E, adding 0.03mol/L of cadmium acetate and 0.0006mol/L ([ Al ]]/[Cd]0.02) AlCl3·6H2Dissolving O in 75ml of deionized water to prepare a solution A, and dissolving 0.1mol/L of thiourea in 10ml of deionized water to prepare a solution B;
step F, adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath;
step G, vertically placing the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature;
step H, after the reaction in step G is finished, taking out the sample, repeatedly washing the sample with deionized water, and drying the washed silicon wafer in a drying box to finally prepare the aluminum-doped cadmium sulfide/nano-silicon heterostructure array with the doping concentration [ Al ]/[ Cd ] of 0.06(0.06 is the molar concentration ratio of Al ions to Cd ions);
step I, sequentially adopting dilute HCl and hot saturated NaOH solution to remove a yellow cadmium sulfide film and a nano porous silicon columnar array on the surface of one side of a sample until the surface becomes silver gray, exposing a single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid to obtain an aluminum-doped cadmium sulfide/silicon nano heterostructure array;
and step J, depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of the cadmium sulfide and the monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, and obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
The resulting electroluminescence pattern is shown in FIG. 11.
Example three:
a preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode comprises the following steps:
step A, placing the cut P-type heavily-doped monocrystalline silicon piece into an acetone or ethanol solution for soaking to remove surface organic pollutants, and then carrying out deep cleaning on the silicon piece by using a standard RCA cleaning process;
b, fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid into the reaction kettle;
step C, putting the reaction kettle into a drying box, and performing heating treatment and heat preservation treatment;
d, taking out the silicon wafer from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array;
step E, 0.03mol/L of cadmium acetate and 0.003mol/L of ([ Al ]]/[Cd]Is 0.1) AlCl3·6H2Dissolving O in 75ml of deionized water to prepare a solution A, and dissolving 0.1mol/L of thiourea in 10ml of deionized water to prepare a solution B;
step F, adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath;
step G, vertically placing the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature;
step H, after the reaction in step G is finished, taking out the sample, repeatedly washing the sample with deionized water, and drying the washed silicon wafer in a drying box to finally prepare the aluminum-doped cadmium sulfide/nano-silicon heterostructure array with the doping concentration [ Al ]/[ Cd ] of 0.06(0.06 is the molar concentration ratio of Al ions to Cd ions);
step I, sequentially adopting dilute HCl and hot saturated NaOH solution to remove a yellow cadmium sulfide film and a nano porous silicon columnar array on the surface of one side of a sample until the surface becomes silver gray, exposing a single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid to obtain an aluminum-doped cadmium sulfide/silicon nano heterostructure array;
and step J, depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of the cadmium sulfide and the monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, and obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
The resulting electroluminescence pattern is shown in FIG. 12.
The invention has the beneficial effects that: the invention aims to provide a novel semiconductor nano-film silicon-based heterojunction light-emitting diode with good luminous efficiency in a visible light wave band, and the novel heterostructure array light-emitting diode is formed by compounding a P-type nano-porous silicon columnar array substrate and N-type aluminum-doped nano cadmium sulfide. The result shows that the proper amount of Al is doped to effectively improve the uniformity and compactness of the cadmium sulfide nano film, increase the carrier mobility and reduce the square resistivity of the film. The novel light-emitting diode constructed by organically combining the aluminum-doped cadmium sulfide nano film and the nano porous silicon columnar array can fully utilize the array and the porous structure of the nano porous silicon columnar array, and a large amount of nano heterojunction can be formed after the combination of the array and the porous structure. Each heterojunction can be a carrier transmission channel, and simultaneously, the doped cadmium sulfide and the higher carrier mobility of the nano porous silicon columnar array are utilized, so that the carrier recombination efficiency can be effectively increased, and the light emitting efficiency of the light emitting diode is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode is characterized by comprising the following steps:
step A, placing the cut P-type heavily-doped monocrystalline silicon piece into an acetone or ethanol solution for soaking to remove surface organic pollutants, and then carrying out deep cleaning on the silicon piece by using a standard RCA cleaning process;
b, fixing the cleaned silicon wafer on a sample rack, vertically placing the silicon wafer into a hydrothermal reaction kettle, and injecting prepared corrosive liquid into the reaction kettle;
step C, putting the reaction kettle into a drying box, and performing heating treatment and heat preservation treatment;
d, taking out the silicon wafer from the drying box, cooling for 60 minutes, opening the cover, cooling to room temperature, taking out the corroded silicon wafer from the reaction kettle, repeatedly washing the silicon wafer with deionized water, and naturally airing to obtain the nano porous silicon columnar array;
step E, 0.03mol/L of cadmium acetate and 0.0018mol/L of [ Al]/[Cd]AlCl of 0.063·6H2Dissolving O in 75ml of deionized water to prepare a solution A, and dissolving 0.1mol/L of thiourea in 10ml of deionized water to prepare a solution B;
step F, adding the solution A and 15ml of ammonia water into a reaction beaker at the same time, and heating to 65 ℃ in a water bath; adding the solution B into a reaction beaker, and heating to 70 ℃ in a water bath;
step G, vertically placing the substrate P-type nano porous silicon columnar array into a reaction solution, and heating at constant temperature;
step H, after the reaction in step G is finished, taking out the sample, repeatedly washing the sample by using deionized water, and drying the cleaned silicon wafer in a drying box to finally prepare the aluminum-doped cadmium sulfide/nano silicon heterostructure array with the doping concentration [ Al ]/[ Cd ] of 0.06;
step I, sequentially adopting dilute HCl and hot saturated NaOH solution to remove a yellow cadmium sulfide film and a nano porous silicon columnar array on the surface of one side of a sample until the surface becomes silver gray, exposing a single crystal Si sheet, and finally washing with deionized water for multiple times to remove the residual liquid to obtain an aluminum-doped cadmium sulfide/silicon nano heterostructure array;
and step J, depositing an ITO layer with the thickness of 150nm and an aluminum layer with the thickness of 500nm on the surfaces of the cadmium sulfide and the monocrystalline silicon by adopting a direct-current magnetron sputtering method and a vacuum evaporation method respectively to serve as a top electrode and a bottom electrode, and obtaining the aluminum-doped cadmium sulfide/nano porous silicon columnar array light-emitting diode.
2. The method for preparing a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode as claimed in claim 1, wherein the time for soaking the P-type heavily doped monocrystalline silicon piece cut in the step A in an acetone or ethanol solution is 5 minutes.
3. The method for preparing the high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode as claimed in claim 1, wherein the etching solution in the step B is composed of 0.03mol/L ferric nitrate nonahydrate, 13mol/L hydrofluoric acid and deionized water, and the filling degree of the reaction kettle is 83%.
4. The method for preparing a high-performance aluminum-doped cadmium sulfide silicon-based heterojunction light-emitting diode according to claim 1, wherein the temperature of the temperature rise treatment in the step C is 142 ℃, and the heat preservation time is 45 minutes.
5. The method as claimed in claim 1, wherein the constant temperature heating in step G is 40 minutes.
6. The method as claimed in claim 1, wherein the temperature in the drying oven in step H is 80 ℃ and the drying time is 20 minutes.
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