CN103159410A - Hydrothermal preparation method of p-type sulfur/silver codoped zinc oxide film - Google Patents
Hydrothermal preparation method of p-type sulfur/silver codoped zinc oxide film Download PDFInfo
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- CN103159410A CN103159410A CN2013100814645A CN201310081464A CN103159410A CN 103159410 A CN103159410 A CN 103159410A CN 2013100814645 A CN2013100814645 A CN 2013100814645A CN 201310081464 A CN201310081464 A CN 201310081464A CN 103159410 A CN103159410 A CN 103159410A
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Abstract
The invention provides a hydrothermal preparation method of a p-type sulfur/silver codoped zinc oxide film, belonging to the fields of optoelectronic semiconductors and nano materials. The preparation method comprises the following steps: by taking water as solvent, zinc nitrate or zinc acetate or a mixture of zinc nitrate and zinc acetate as a zinc source, pyridine and n-butylamine as alkali sources, tetramethylthiourea as a sulfur source, silver chloride or silver nitrate as a silver source, ammonium nitrate as regulator and nitrogen gas or argon gas as blanketing gas, through a medium-low-temperature hydrothermal synthesis technology, epitaxially growing a ZnO film containing Ag and S on a substrate with a previously prepared ZnO seed crystal layer; and then, rinsing the surface of the film with deionized water, and drying in a thermostatic oven of 120 DEG C for 10 minutes, thus finally obtaining the p-type sulfur/silver codoped zinc oxide film having hexagonal structure and high preferential orientation along the c axis. According to the invention, the preparation process is simple, the preparation cost is low, and the p-type sulfur/silver codoped zinc oxide film having satisfactory crystal quality and electric property can be prepared repeatedly.
Description
Technical field
The present invention relates to a kind of Hydrothermal Synthesis technology of utilizing and prepare the method that p-type sulphur silver is mixed zinc-oxide film altogether, belong to optoelectronic semiconductor and field of nanometer material technology.
Background technology
Zinc oxide (ZnO) is a kind of wide bandgap semiconductor materials, about 3.3 eV of band gap under room temperature, exciton bind energy, up to 60 meV, is considered to prepare the ideal material of blue light and ultraviolet light-emitting diodes (LED) and laser diode (LD), at optoelectronic areas, important application is arranged.But, owing to there being many intrinsic alms giver's defects in non-blended ZnO, to p-type, doping produces very strong self compensation, make p-type ZnO preparation difficulty, become and affect the bottleneck of ZnO in the photoelectric field application.For over ten years, both at home and abroad the scientific worker is with IA family (Li, Na), VA family (N, P
,as, Sb) and IB(Cu, Ag) carried out the research work of a large amount of ZnO p-type doping for the acceptor doping element, although make great progress, also exist prepared p-type ZnO hole low by (approximately 10
16cm
-3), electrical stability is poor, repeatable low problem.This be mainly due to: 1, under the epuilibrium thermodynamics condition, recipient element solid solubility in ZnO is low, is even zero, therefore, when utilizing the physical method doping, need under the non-equilibrium thermodynamics condition, carry out, and causes poor controllability, repeatable low; 2, the acceptor level be doped in ZnO is dark, causes electric property and poor stability thereof; 3, there is the donor doping state in some recipient elements, thus the self compensation effect produced.As, when the Li doping ZnO, exist Li for the Zn Li gap alms giver that advocated peace simultaneously, the latter compensates the former, causes being difficult to obtain p-type ZnO.Recently, theoretical investigation shows that IB family element is when ZnO doping, and the element substitution Zn of IB family becomes the acceptor, as interstitial atom, becomes the alms giver, and the formation of the element substitution Zn of IB family can be much smaller than the formation energy of its interstitial atom, this means that the IB doping can avoid the self compensation problem of recipient element.At IB family element, in ZnO doping, Ag substitutes Zn(Ag
zn) acceptor level (0.4 eV) is less than Cu and substitutes Zn(0.7 eV) and the alternative Zn(0.5 eV of Au), so, the acceptor doping element that Ag has been in IB family.But, for the p-type doping, 0.4 eV acceptor level is too dark, is difficult to realize p-type electric-conducting; And Ag is very little in the solid solubility of ZnO, be unfavorable for the p-type doping, therefore, obtain the p-type ZnO of Ag doping, improve the doping content of Ag in ZnO, reducing its acceptor level is key issue.Theoretical and experiment shows, the alternative O(S of a small amount of S
o) be doped to the top of valence band energy level that can promote ZnO in ZnO, and, on almost not impact at the bottom of the conduction band of ZnO, this is expected to reduce Ag acceptor's energy level; And Ag
znand S
ocan form ionization energy and compare Ag
znbe subject to main much smaller Ag
zn-nS
o(n=1,2,3,4) compound acceptor, this will more be conducive to obtain p-type ZnO.In addition, because Ag more easily is combined with S than Zn, so S improves the solid solubility of Ag in ZnO doped with being beneficial to.Therefore, taking Ag and S codoped may be the effective way that obtains p-type ZnO.
In recent years, people utilize magnetron sputtering technique to carry out p-type Ag-S to mix altogether ZnO zinc-oxide film (ZnO:(Ag, S)) research work prepared as: the people such as Sun utilize magnetron sputtering technique, make target with the ZnS target with containing Ag 1 at.%, deposit Ag silver doped zinc sulphide (ZnS) film that approximately 350 nm are thick on the silicon substrate of 300 ℃ under the argon gas atmosphere of 4 Pa, then 600 ~ 1000 ℃ of lower thermooxidizings 4 hours, obtain ZnO:(Ag, S) film (L.J. Sun, et al., Solid State Communications 149 (2009) 1663-1665), the people such as Li utilize the magnetron sputtering surface to be placed with the ZnO target of ZnS target and filamentary silver, deposit ZnO:(Ag on quartz substrate under oxygen and argon gas atmosphere, S) film, and in conjunction with later stage thermal treatment, obtain p-type ZnO:(Ag, S) film (J.C. Li et al., Journal of Alloys and Compounds 550 (2013) 479 – 482).But need to carry out later stage thermal treatment in magnetron sputtering method, although this has improved the quality of crystal, the Ag silver that also can make part be doped in ZnO is separated out, and is unfavorable for the p-type doping.
During the present invention will utilize, the low-temperature hydrothermal synthetic technology prepares the Ag-S co-doping p-type ZnO.Because Ag and S are doped in ZnO in chemical reaction, do not need to carry out later stage thermal treatment, thereby be conducive to improve Ag doping content in ZnO.In addition, with respect to magnetron sputtering method, hydrothermal synthesis method also has that the simple cost of equipment is low, and preparation technology is simple, the advantage that preparation cost is cheap.But, utilize hydrothermal method to prepare Ag-S and mix altogether ZnO and also exist existing system not to be suitable for Ag-S to mix altogether problem prepared by ZnO.Existing system is divided and is mainly contained organic alkali source system by alkali source, comprises the organic amine alkali systems, as urotropin, hexahydroaniline are made the system of alkali source; Inorganic alkali source system, as ammoniacal liquor, sodium hydroxide, potassium hydroxide are made the system of alkali source; Without the alkali source system, as only with zinc acetate, made the system of the synthetic ZnO in source.Due to Ag
+easily be reduced in basic solution, easily be reduced agent reduction in solution, therefore, find in neutral or neutral meta-alkali and solution without the condition of reductive agent under synthetic ZnO:(Ag, S) film is key issue of the present invention.
Summary of the invention
The object of the invention is to adopt the Hydrothermal Synthesis technology, realize Ag and S codoped in ZnO, solve Ag doping content in ZnO low, the problem that acceptor level is dark, prepare p-type Ag-S and mix altogether ZnO film.
The present invention is characterized in that take that water is as solvent, and zinc nitrate or zinc acetate or zinc nitrate and zinc acetate mixture are the zinc source, and pyridine, n-Butyl Amine 99 are alkali source, tetramethyl thiourea is the sulphur source, silver chloride or Silver Nitrate are silver-colored source, and ammonium nitrate is conditioning agent, and nitrogen or argon gas are for filling gas; Low-temperature hydrothermal synthetic technology in employing, the ZnO film that epitaxy contains Ag and S on the substrate of the previously prepared ZnO of having inculating crystal layer; Then use the deionized water rinsing film surface, and in 120 ℃ of thermostat containers dry 10 min, can obtain p-type Ag-S and mix altogether ZnO film.Prepared p-type ZnO:(Ag, S) film has hole concentration ~ 10
17cm
-3, technological process as shown in Figure 1.
Implementation process of the present invention is as follows:
A kind of p-type ZnO:(Ag, S) hydrothermal preparing process of film, take water as solvent, zinc nitrate or zinc acetate or zinc nitrate and zinc acetate mixture are the zinc source, pyridine, n-Butyl Amine 99 are alkali source, and tetramethyl thiourea is the sulphur source, and silver chloride or Silver Nitrate are silver-colored source, ammonium nitrate is conditioning agent, and nitrogen or argon gas are for filling gas; Consumption in molar ratio, zinc nitrate: zinc acetate=1:1-x, wherein 0≤x≤1, (zinc nitrate+zinc acetate) in molar ratio: tetramethyl thiourea: ammonium nitrate=1:0.5 ~ 2:0.5 ~ 2, (zinc nitrate+zinc acetate) in molar ratio: silver chloride or Silver Nitrate=1:0.002 ~ 0.03; Its preparation process is, with 37 ml deionized waters ,Yin source, ,Liu source, solving zinc source and conditioning agent under supersound process, and adds 0.3 ml pyridine in solution, obtains reaction solution; Add 0.5 ~ 3.0 ml n-Butyl Amine 99 in 5 ml volumetric flasks, and to supply cumulative volume with pyridine be 5 ml, obtain alkali lye; The substrate with the ZnO seed crystal that on support prepared by the clamping sol-gel method (as: common slide glass, quartz, Si, sapphire etc.); Support, volumetric flask are placed in the reactor inner bag, add reaction solution, as shown in Figure 2; Be filled with nitrogen or argon gas to the reactor inner bag, the envelope still, after reactor being placed in the thermostatic drying chamber that is heated in advance 160 ℃, be warmed up to 190 ℃, keeps 0.5 ~ 2 h; After reaction finishes, take out the substrate of the film of having grown, with after the deionized water rinsing film, dry 10 min in 120 ℃ of thermostat containers, obtain hexagonal structure and along p-type ZnO:(Ag, the S of c-axis height preferential growth) film.
Principal reaction equation of the present invention is:
AgCl + 3TMTM → [Ag(TMTM)
3]
+ + Cl
-
TMTM + H
2O → TMU + H
2S
[Ag(TMTM)
3]
+ + 2H
2O → [Ag(HS)
2]
- + 2TMU + TMTM + 2H
+
NH
4 + + C
5H
5N NH
3 + C
5H
6N
+
NH
4 + + CH
3(CH
2)
3NH
2 → NH
3 + CH
3(CH
2)
3NH
3 +
NH
3 + H
2O NH
4 + + OH
-
Zn
2+ + OH
- → Zn(OH)
2
Zn(OH)
2 ZnO + H
2O
ZnO + [Ag(HS)
2]
- → ZnO:(Ag, S) + 2OH
-
Wherein, TMTM, TMU, C
5h
5n, CH
3(CH
2)
3nH
2be respectively tetramethyl thiourea, tetramethyl-urea, pyridine, n-Butyl Amine 99.
Innovative point of the present invention: 1, adopt the hydrothermal method synthetic technology to prepare Ag-S and mix altogether ZnO film; 2, adopt new Hydrothermal Synthesis system, comprise alkali lye is separated with reaction solution, selecting tetramethyl thiourea is the sulphur source, near liquid level place synthetic film, and selects normal temperature and pressure boiling point n-Butyl Amine 99 and normal temperature and pressure boiling point than the water high pyridine lower than water to make alkali source simultaneously.
Ag-S provided by the invention mixes ZnO film preparation method's advantage altogether:
(1) preparation technology is simple, favorable repeatability, but large area deposition film.
(2) preparation cost (comprising equipment and starting material) is low.
(3) do not need to carry out the high-temperature heat treatment in later stage, avoided Ag to mix ZnO and separate out altogether from Ag-S.
(4) select tetramethyl thiourea to do the sulphur source, it decomposes slowly, and hydrolysis only discharges hydrogen sulfide, easy controlled doping element.
(5) reaction solution separates with alkali lye, easily controls the basicity of reaction solution.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is reactor internal structure schematic diagram of the present invention.In figure, 1 is polytetrafluoroethylliner liner; 2 is substrate; 3 is the tetrafluoroethylene support; 4 is volumetric flask; 5 is liquid level; 6 is reaction solution; 7 is alkali lye.
Fig. 3 is the X-ray diffractogram of the ZnO thin film doped sample of S that makes of example 1 of the present invention.
Fig. 4 is the ultraviolet-visible photoabsorption figure of the ZnO thin film doped sample of S that makes of example 1 of the present invention.
Fig. 5 is the X-ray diffractogram that Ag-S that example 2 of the present invention makes mixes the ZnO film sample altogether.
Fig. 6 is that the Ag-S that example 2 of the present invention makes mixes Zn in the ZnO film sample altogether, O, the XPS spectrum of S and Ag.
Fig. 7 is the scanning electron microscope (SEM) photograph that Ag-S that example 2 of the present invention makes mixes the ZnO film sample altogether.
Fig. 8 is the ultraviolet-visible photoabsorption figure that Ag-S that example 2 of the present invention makes mixes the ZnO film sample altogether.
Fig. 9 is the 89K low-temperature photoluminescence figure that Ag-S that example 2 of the present invention makes mixes the ZnO film sample altogether.
Embodiment
Example of the present invention substrate used is the slide glass (7 mm * 5 mm * 1 mm) with the ZnO inculating crystal layer, can prepare by sol-gel method by the ZnO inculating crystal layer; Film growth apparatus used is the stainless steel cauldron that includes 100 ml polytetrafluoroethylliner liner.By 0.812 g Zinc diacetate dihydrate, 0.296 g ammonium nitrate, 0.537 g tetramethyl thiourea medicine, take and be placed in same beaker with analytical balance, add 37 ml deionized waters in beaker, with ultrasonication 10 min, promote solid medicine to dissolve, remove the oxygen contained in water body simultaneously; Add 0.3 ml pyridine in beaker, obtain reaction solution.By the substrate aufwuchsplate be clamped in down the self-control support on, support can guarantee the substrate horizontal positioned, and with the reaction solution upper surface on same height; 2.5 ml n-Butyl Amine 99s are added in 5 ml volumetric flasks, and to supply cumulative volume with pyridine be 5 ml.Over against being positioned in reactor, (substrate is positioned at middle) on support and volumetric flask.Shift reaction liquid, in reactor, is filled with nitrogen in reactor, and the envelope still, after reactor being placed in the thermostatic drying chamber that is heated in advance 160 ℃, be warmed up to 190 ℃, keeps 1 h; Take out reactor, open in 15 min, take out the long substrate that film is arranged; Use the deionized water rinsing film, and be placed on 120 ℃ of drying 10 min in loft drier, can obtain S ZnO thin film doped.XRD tests and shows, film is to have hexagonal structure the edge c-axis direction preferred orientation vertical with substrate, as shown in Figure 3; UV, visible light photoabsorption test points out that the ZnO thin film doped optical band gap of prepared S is 3.16 eV, as shown in Figure 4.
Example of the present invention substrate used is the quartz plate (7 mm * 5 mm * 1 mm) with the ZnO inculating crystal layer, can prepare by sol-gel method by the ZnO inculating crystal layer; Film growth apparatus used is the stainless steel cauldron that includes 100 ml polytetrafluoroethylliner liner.By 0.275 g zinc nitrate hexahydrate, 0.609 g Zinc diacetate dihydrate, 0.296 g ammonium nitrate, 0.489 g tetramethyl thiourea, 0.027 g silver chloride medicine, with analytical balance, take, and be placed in same beaker, add 37 ml deionized waters in beaker, with ultrasonication 10 min, promote solid medicine to dissolve, remove the oxygen contained in water body simultaneously; Add 0.3 ml pyridine in beaker, obtain reaction solution; By the substrate aufwuchsplate be clamped in down the self-control support on, support can guarantee the substrate horizontal positioned, and with the reaction solution upper surface on same height.2.5 ml n-Butyl Amine 99s are added in 5 ml volumetric flasks, and to supply cumulative volume with pyridine be 5 ml.Over against being positioned in reactor, (substrate is positioned at middle) on support and volumetric flask.Shift reaction liquid, in reactor, is filled with argon gas in reactor, and the envelope still, after reactor being placed in the thermostatic drying chamber that is heated in advance 160 ℃, be warmed up to 190 ℃, keeps 1 h; Take out reactor, open in 15 min, take out the long substrate that film is arranged, use the deionized water rinsing film surface, then be placed on 120 ℃ of drying 10 min in loft drier, can obtain Ag-S and mix altogether ZnO film.XRD tests and shows, film is to have hexagonal structure the edge c-axis direction preferred orientation vertical with substrate, as shown in Figure 5; The XPS test shows in film to contain Zn, O, and S and Ag, as shown in Figure 6, its content is respectively 40.54 at.%, 52.95 at.%, 4.68 at.% and 1.83 at.%; Scanning electron microscope and photoluminescence are tested and are shown, film has good crystal mass and luminescent properties, as Fig. 6 and 9.By Hall effect, test to such an extent that film is p-type electric-conducting, carrier concentration is ~ 10
17cm
-3, as shown in table 1
.utilizing the UV, visible light photoabsorption to record prepared sulphur silver, to mix altogether the ZnO film optical band gap be 3.17 eV, as shown in Figure 8.
The Ag-S that table 1 example 2 of the present invention makes mixes the varying magnetic field hall measurement result of ZnO film sample altogether
| Field [G] | Resistivity [ohm·cm] | Type | Carrier Density [1/cm3] | Hall Mobility [cm2/(VS)] |
| 3.00E+03 | 5.98E+01 | p | 4.60E+18 | 2.31E-02 |
| 6.00E+03 | 5.98E+01 | p | 6.28E+17 | 1.69E-01 |
| 9.00E+03 | 5.97E+01 | p | 8.20E+17 | 1.30E-01 |
| 1.20E+04 | 5.96E+01 | p | 3.10E+17 | 3.43E-01 |
Claims (4)
1. the preparation method that p-type sulphur silver is mixed zinc-oxide film altogether, it is characterized in that take that water is as solvent, zinc nitrate or zinc acetate or zinc nitrate, zinc acetate are the zinc source, pyridine, n-Butyl Amine 99 are alkali source, tetramethyl thiourea is the sulphur source, silver chloride or Silver Nitrate are silver-colored source, and ammonium nitrate is conditioning agent, and nitrogen or argon gas are for filling gas; The solid medicine consumption in molar ratio, zinc nitrate: zinc acetate=1:1-x, 0≤x≤1 wherein, (zinc nitrate+zinc acetate) in molar ratio: tetramethyl thiourea: ammonium nitrate=1:0.5 ~ 2:0.5 ~ 2, (zinc nitrate+zinc acetate) in molar ratio: silver chloride or Silver Nitrate=1:0.002 ~ 0.03; Take middle low-temperature hydrothermal synthesis method as the reaction means, the ZnO film that epitaxy p-type sulphur silver is mixed altogether on the substrate of the previously prepared ZnO of having inculating crystal layer.
2. the preparation method that a kind of p-type sulphur silver according to claim 1 is mixed zinc-oxide film altogether, it is characterized in that: the described reaction times is 0.5 ~ 2 h.
3. the preparation method that a kind of p-type sulphur silver according to claim 1 is mixed zinc-oxide film altogether is characterized in that: described is that alkali lye is separated with reaction solution.
4. the preparation method that a kind of p-type sulphur silver according to claim 1 is mixed zinc-oxide film altogether is characterized in that: described is to synthesize ZnO film under the reaction solution liquid level in 0 ~ 2 cm depth range.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367639A (en) * | 2013-07-25 | 2013-10-23 | 福州大学 | Zinc oxide nanowire low-power consumption resistive random access memory and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| KR20100022144A (en) * | 2008-08-19 | 2010-03-02 | 전남대학교산학협력단 | Method for manufacturing zinc oxide thin film having control of surface morphology and the zinc oxide thin film thereby |
| CN102626625A (en) * | 2012-03-14 | 2012-08-08 | 中国人民解放军第二炮兵工程学院 | Precious metal-doped ZnO nanoscale particles and use of the precious metal-doped ZnO nanoscale particles as photocatalyst for unsymmetrical dimethylhydrazine wastewater degradation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100022144A (en) * | 2008-08-19 | 2010-03-02 | 전남대학교산학협력단 | Method for manufacturing zinc oxide thin film having control of surface morphology and the zinc oxide thin film thereby |
| CN102626625A (en) * | 2012-03-14 | 2012-08-08 | 中国人民解放军第二炮兵工程学院 | Precious metal-doped ZnO nanoscale particles and use of the precious metal-doped ZnO nanoscale particles as photocatalyst for unsymmetrical dimethylhydrazine wastewater degradation |
Non-Patent Citations (2)
| Title |
|---|
| QIXIN WAN ET AL: "Theory study of Ag-S codoping in ZnO", 《JOURNAL OF PHYSICS: CONFERENCE SERIES》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367639A (en) * | 2013-07-25 | 2013-10-23 | 福州大学 | Zinc oxide nanowire low-power consumption resistive random access memory and preparation method thereof |
| CN103367639B (en) * | 2013-07-25 | 2015-09-09 | 福州大学 | A kind of Zinc oxide nanowire low-power consumption resistance-variable storing device and preparation method thereof |
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