CN103560156A - Preparation method of Zn[1-y]Mn[y]Te[1-x]O[x] sol and Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film and application of Zn[1-y]Mn[y]Te[1-x]O[x] sol and Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film - Google Patents
Preparation method of Zn[1-y]Mn[y]Te[1-x]O[x] sol and Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film and application of Zn[1-y]Mn[y]Te[1-x]O[x] sol and Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000002738 chelating agent Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 37
- 239000001301 oxygen Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 6
- 239000008118 PEG 6000 Substances 0.000 claims description 5
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007792 addition Methods 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000000137 annealing Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910007709 ZnTe Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910017231 MnTe Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
Abstract
The invention relates to a preparation method of Zn[1-y]Mn[y]Te[1-x]O[x] sol and Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film and application of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film. The preparation method of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film specifically comprises the steps that a low-temperature processing method is adopted, Mn(CH3COO)2 4H2O and Zn(CH3COO)2 2H2O serve as raw materials, stabilizers, dispersants, chelating agents, cross-linking agents and deionized water are added, full dissolution is carried out through magnetic stir, the obtained solution is mixed with a tri-n-octylphosphine telluride solution, the PH value is adjusted through addition of ammonium hydroxide in a dripping mode, a Zn(NO3)2 solution is added in a dripping mode, mixing is carried out, a reaction is carried out at the temperature of 240DEG C, and the Zn[1-y]Mn[y]Te[1-x]O[x] sol is obtained through cooling; then, the obtained Zn[1-y]Mn[y]Te[1-x]O[x] sol is added to a monocrystalline wafer which is cleaned in advance in a dripping mode, coating is evenly carried out, infrared heating is carried out, heat treatment is carried out at the temperature of 300DEG C, dripping addition, coating and heating are repeatedly carried out to form the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film, and finally annealing treatment is carried out on the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film at the temperature of 400DEG C to improve the surface performance of the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film. A sol gel combined rotary coating technology is adopted in the preparation method of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film and application of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film, the technology is simple, the temperature is lower, and is about 250DEG C, and the preparation method of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film and application of the Zn[1-y]Mn[y]Te[1-x]O[x] sol and the Zn[1-y]Mn[y]Te[1-x]O[x] middle strip film are applicable to large-scale production.
Description
Technical field
The invention belongs to technical field of solar batteries.Particularly, the present invention relates to a kind of zinc-manganese tellurium oxygen (Zn
1-ymn
yte
1-xo
x) preparation method of colloidal sol, the zinc-manganese tellurium oxygen (Zn that this colloidal sol is raw material of take
1-ymn
yte
1-xo
x) middle membrane preparation method and this colloidal sol and middle membrane application.
Background technology
Solar cell is one of effective way of utilizing solar energy, but utilizes cheap and abundant solar power generation is still difficult to realize at present, is because the cost of solar cell is too expensive on the one hand, is lower to the utilization ratio of solar energy on the other hand.At present, fully absorbing a kind of important method that sunlight improves efficiency of solar cell is to adopt many knot laminated construction, and way is that the different two or more sub-battery of band gap is cascaded successively by band gap size conventionally.Its essence is equivalent to solar spectrum to be divided into several sections, and each sub-battery absorbs and immediate that section of light of its band gap.So both increased the absorptivity to low energy end spectrum, and reduced again the energy loss of high-energy photons, the advantage that improves battery efficiency is clearly.But in actual process, between each sub-battery, run into a series of problem: current-unbalance, interface exist a large amount of defect complex centres, low resistance connection etc. cause battery reliability and processing compatibility poor.
Intermediate Gray semi-conducting material can effectively solve the problem that sunlight fully absorbs, and is the most important part of Intermediate Gray efficient solar battery.When illumination is mapped to Intermediate Gray semi-conducting material, energy of Electron absorption is higher than band gap E
gphoton directly from valence band, transit to conduction band, also can absorb respectively two energy lower than band gap E
gphoton from valence band, via Intermediate Gray, enter conduction band again.Visible Intermediate Gray has played the springboard effect of electronics from valence band to conduction band, can increase the absorption of material to long-wave band photon.Manufacture Intermediate Gray solar battery structure simple, only intermediate zone material need to be clipped between traditional p-type and N-shaped semiconductor, itself and electrode are separated, at electronics, from conduction band, be extracted to n district like this, when hole is extracted to p district from valence band, charge carrier can not be collected by Intermediate Gray.Therefore, Intermediate Gray can not reduce open circuit voltage when improving battery short circuit electric current, and open circuit voltage is still determined by the band gap of material of main part.Because Intermediate Gray solar cell can utilize sunlight efficiently, the conversion efficiency of single-unit Intermediate Gray solar cell is suitable with the transformation efficiency that more piece tradition pn ties the solar cell of connecting.
Although Intermediate Gray solar cell has outstanding advantage utilizing aspect solar energy, suitable intermediate zone material is still among research and discovery.Mainly in the basic problem that need to solve due to Intermediate Gray solar cell, most critical be efficient absorption and the conversion of light, therefore Intermediate Gray solar cell has harsh requirement to intermediate zone material efficiently, for example: in order to make electronics be smoothly through Intermediate Gray transition, Intermediate Gray should be that part is filled up and isolated being present among host's semiconductor band gap; In addition, to Intermediate Gray, absorption coefficient of light of the level of energy in host's semiconductor and each energy band-to-band transition etc. physical characteristic relevant to Intermediate Gray has strict requirement.
High mismatch alloy is a kind of new material, substituted element and be substituted the electronegativity difference that between element, existence is larger.As in III-V compound, the nitrogen element that V group element is partly diluted replaces, or the oxygen element being partly diluted at II-VI compound Zhong， VI family element replacement, forms high mismatch alloy.Replacing atom and being substituted electronegativity difference larger between atom causes its uncommon band structure to explain with anti-cross band model.According to this model, the expansion state of the local state that N or O are relevant and host's semi-conducting material interacts, and determines the Energy band electron structure of high mismatch alloy.Anti-cross band model prophesy: if localized state energy level just lower than conduction band edge, just has an arrowband to form in forbidden band.The people such as the K.M.Yu of Univ California-Berkeley based on being with anti-cross model (band anticrossing, BAC), introduced ZnTe, MnTe and Zn by the method for laser molecular beam epitaxy by O as far back as 2002～2003 years
1-ymn
yte part substitute Te wherein, form high mismatch alloy intermediate zone material ，Dui II-O-VI family semi-conducting material and have carried out early-stage Study, for effective absorption that electronegativity difference causes Intermediate Gray and then promotes light is laid a good foundation.
At Zn
1-ymn
yte
1-xo
xin middle membrane preparation, mainly contain at present following several method: Laser Molecular Beam Epitaxy (MBE), metal organic vapor phase epitaxy method (MOCVD), microwave magnetically controlled sputter method and pulsed laser deposition technology and spraying high temperature pyrolysis etc.But these method complex process, cost is higher, and harsh to equipment requirement.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of technique is simple, with low cost, be applicable to suitability for industrialized production zinc-manganese tellurium oxygen colloidal sol and the middle membrane preparation method of zinc-manganese tellurium oxygen and this colloidal sol and middle membrane application.
On the one hand, the invention provides a kind of preparation method of zinc-manganese tellurium oxygen colloidal sol, described zinc-manganese tellurium oxygen colloidal sol is Zn
1-ymn
yte
1-xo
xcolloidal sol, wherein, 0 < x < 1,0 < y < 1, described preparation method comprises the following steps:
(1) under inert gas, in tellurium powder, add tri octyl phosphine solution, seal ultrasonic processing 45 minutes～60 minutes, obtain tellurium tri octyl phosphine solution, be designated as solution I; Wherein, the mol ratio of described tellurium powder and tri octyl phosphine solution is 1:45～1:90, and the molar concentration of tri octyl phosphine solution is 25mmol/L～50mmol/L;
(2) Mn (CH that is 6:520～30:540 by mass ratio
3cOO)
24H
2o powder and Zn (CH
3cOO)
22H
2o powder mixes, stabilizer, dispersant, chelating agent, crosslinking agent and deionized water that interpolation volume ratio is 1:3:1:1:5, and magnetic agitation, dissolving, then drip ammoniacal liquor and regulate pH value to 7.3～7.7, and the solution that obtains mixing, is designated as solution II; In this step, the unit of measurement of quality and volume can be mg and mL, for example Mn (CH
3cOO)
24H
2o powder 6～30mg, Zn (CH
3cOO)
22H
2o520～540mg, stabilizer is 5mL, dispersant 15mL, chelating agent 5mL, crosslinking agent and deionized water 25mL;
(3) Zn (NO that to add with described mixeding liquid volume in the solution I that is 1:1 to volume ratio and the mixed liquor of II be 0.5mol/L than the molar concentration that is 1～3:22～24
3)
2, at 240 ℃, react 1～1.5 hour, obtain described zinc-manganese tellurium oxygen colloidal sol.
In above-mentioned preparation method, described stabilizer is diethanol amine, and described dispersant is absolute ethyl alcohol, and described chelating agent is citric acid, and described crosslinking agent is PEG6000.
On the other hand, the present invention also provides the application of a kind of as prepared by above-mentioned preparation method zinc-manganese tellurium oxygen colloidal sol in zinc-manganese tellurium oxygen Intermediate Gray film.
Another aspect, the present invention also provides the application of a kind of as prepared by above-mentioned preparation method zinc-manganese tellurium oxygen colloidal sol in solar cell.
Again on the one hand, the present invention also provides a kind of zinc-manganese tellurium oxygen middle membrane preparation method, and described zinc-manganese tellurium oxygen Intermediate Gray film is Zn
1-ymn
yte
1-xo
xintermediate Gray film, wherein, 0 < x < 1,0 < y < 1, described preparation method comprises the following steps:
(1) substrate base is carried out to preliminary treatment, dry rear standby;
(2) zinc-manganese tellurium oxygen colloidal sol is coated in to the substrate base of processing through step (1), described coating speed is 4500～5000 revs/min; Wherein, described zinc-manganese tellurium oxygen colloidal sol is to adopt the preparation method described in claim 1 or 2 to prepare;
(3) substrate base step (2) having been applied carries out infrared baking 30min, then heat treatment 15min at 300 ℃;
(4) repeat above-mentioned coating, infrared baking and heat treatment 5 times, obtain described zinc-manganese tellurium oxygen Intermediate Gray film.
In above-mentioned preparation method, preliminary treatment described in step (1) comprises substrate base is adopted to liquid detergent, deionized water, absolute ethyl alcohol and deionized water ultrasonic cleaning successively.
In above-mentioned preparation method, described substrate base is that purity is more than 99.9999% monocrystalline silicon piece.
In above-mentioned preparation method, described preparation method also comprises: the zinc-manganese tellurium oxygen Intermediate Gray film normal temperature making in step (4) is deposited 48 hours, then at 300 ℃, annealed 1 hour.
Finally, the invention provides the application of a kind of as prepared by above-mentioned preparation method zinc-manganese tellurium oxygen Intermediate Gray film in solar cell.
The present invention does not limit described zinc-manganese tellurium oxygen Intermediate Gray film for the preparation method of solar cell, it will be appreciated by those skilled in the art that everyly zinc-manganese tellurium oxygen Intermediate Gray film all to be can be used for to the present invention for the preparation method of solar cell.
Compared with prior art, the present invention at least has following beneficial effect: the collosol and gel that the present invention adopts is in conjunction with spin coated technology, and technique is simple, temperature lower (approximately 250 ℃), be suitable for large area and produce, and the Zn of preparation
1-ymn
yte
1-xo
xintermediate Gray thin-film material surface is smooth smooth, the polycrystalline state with good properties of crystal lattice, compares the optical absorption characteristics of parent semiconductor ZnTe, has obviously widened the absorption bands of light, there is good absorbing properties, in efficient solar battery of future generation field, there is potential application prospect.
Accompanying drawing explanation
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the atomic force microscope picture on membrane surface in the middle of a preferred embodiment of the invention;
Fig. 2 is membrane X ray diffracting spectrum in the middle of a preferred embodiment of the invention;
Fig. 3 is membrane absorption factor collection of illustrative plates in the middle of a preferred embodiment of the invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, the embodiment providing is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
embodiment 1
1.Zn
0.95mn
0.05te
0.950
0.05the preparation of colloidal sol
(a) the Te powder of 317mg is put into the round-bottomed flask reactor that is full of argon gas, inject the tri octyl phosphine solution that 50mL molar concentration is 25mmol/L, obtain tellurium tri octyl phosphine (TOPTe) homogeneous solution, be designated as solution I;
(b) by stoichiometric proportion, accurately take the Mn (CH of 30mg
3cOO)
24H
2zn (the CH of O, 520mg
3cOO)
22H
2the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, the citric acid of 5mL and the PEG6000 of 5mL put into beaker, and mix with the deionized water of 25mL, and magnetic agitation is fully dissolved, and slowly drips ammoniacal liquor (NH
3h
2o), the pH value of regulator solution is 7.3 to be alkalescent, after mixing, obtains solution II;
(c) then, the cooling solution II of 22mL is mixed with 22mL cooling solution I, drip the Zn (NO that 6mL concentration is 0.025mol/L
3)
2, pack in the 50mL reactor of heat resisting and pressure resisting, control approximately 240 ℃ of temperature, the cooling colloidal sol that obtains after 60 minutes.
2.Zn
0.95mn
0.05te
0.95o
0.05middle membrane preparation
(a) preliminary treatment of substrate base: by the purity that is of a size of 30mm * 50mm * 1mm be more than 99.9999% monocrystalline silicon piece with liquid detergent clean several all over after, adopt successively deionized water, absolute ethyl alcohol, deionized water ultrasonic cleaning, with hair-dryer, the deionized water on glass substrate is dried up standby;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with the speed of 4500 revs/min, be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, then heat treatment 15 minutes in 300 ℃ of Muffle furnaces; Repeat above dropping, coating, baking and heat treatment step 5 times, obtain the Zn of the about 400nm of thickness
0.95mn
0.05te
0.95o
0.05semiconductor film material, then this thin-film material normal temperature is deposited two days, 400 ℃ of Muffle furnaces are annealed 1 hour, finally obtain Zn
0.95mn
0.05te
0.95o
0.05film.
embodiment 2
1.Zn
0.97mn
0.03te
0.97o
0.03the preparation of colloidal sol
(a) the Te powder of 317mg is put into the round-bottomed flask reactor that is full of argon gas, inject the tri octyl phosphine solution that 50mL molar concentration is 30mmol/L, obtain tellurium tri octyl phosphine (TOPTe) homogeneous solution, be designated as solution I;
(b) by stoichiometric proportion, accurately take the Mn (CH of 18mg
3cOO)
24H
2zn (the CH of O, 530mg
3cOO)
22H
2the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, the citric acid of 5mL and the PEG6000 of 5mL put into beaker, and mix with the deionized water of 25mL, and magnetic agitation is fully dissolved, and slowly drips ammoniacal liquor (NH
3h
2o), the pH value of regulator solution is 7.4 to be alkalescent, after mixing, obtains solution II;
(c) then, the cooling solution II of 23mL is mixed with 23mL cooling solution I, drip the Zn (NO that 4mL concentration is 0.025mol/L
3)
2, pack in the 50mL reactor of heat resisting and pressure resisting, control approximately 240 ℃ of temperature, the cooling colloidal sol that obtains after 90 minutes.
2.Zn
0.97mn
0.03te
0.97o
0.03middle membrane preparation
(a) preliminary treatment of substrate base: by the purity that is of a size of 30mm * 50mm * 1mm be more than 99.9999% monocrystalline silicon piece with liquid detergent clean several all over after, adopt successively deionized water, absolute ethyl alcohol, deionized water ultrasonic cleaning, with hair-dryer, the deionized water on glass substrate is dried up standby;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with the speed of 4800 revs/min, be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, then heat treatment 15 minutes in 300 ℃ of Muffle furnaces; Repeat above dropping, coating, baking and heat treatment step 5 times, obtain the Zn of the about 400nm of thickness
0.97mn
0.03te
0.97o
0.03semiconductor film material, then this thin-film material normal temperature is deposited two days, 400 ℃ of Muffle furnaces are annealed 1 hour, finally obtain Zn
0.97mn
0.03te
0.97o
0.03film.
embodiment 3
1.Zn
0.99mn
0.01te
0.99o
0.01the preparation of colloidal sol
(a) the Te powder of 317mg is put into the round-bottomed flask reactor that is full of argon gas, inject the tri octyl phosphine solution that 50mL molar concentration is 50mmol/L, obtain tellurium tri octyl phosphine (TOPTe) homogeneous solution, be designated as solution I;
(b) by stoichiometric proportion, accurately take the Mn (CH of 6mg
3cOO)
24H
2zn (the CH of O, 540mg
3cOO)
22H
2the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, the citric acid of 5mL and the PEG6000 of 5mL put into beaker, and mix with the deionized water of 25mL, and magnetic agitation is fully dissolved, and slowly drips ammoniacal liquor (NH
3h
2o), the pH value of regulator solution is 7.5 to be alkalescent, after mixing, obtains solution II;
(c) then, the cooling solution II of 24mL is mixed with 24mL cooling solution I, drip the Zn (NO that 2mL concentration is 0.025mol/L
3)
2, pack in the 50mL reactor of heat resisting and pressure resisting, control approximately 250 ℃ of temperature, the cooling colloidal sol that obtains after 90 minutes.
2.Zn
0.99mn
0.01te
0.99o
0.01middle membrane preparation
(a) preliminary treatment of substrate base: by the purity that is of a size of 30mm * 50mm * 1mm be more than 99.9999% monocrystalline silicon piece with liquid detergent clean several all over after, adopt successively deionized water, absolute ethyl alcohol, deionized water ultrasonic cleaning, with hair-dryer, the deionized water on glass substrate is dried up standby;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with the speed of 5000 revs/min, be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, then heat treatment 15 minutes in 300 ℃ of Muffle furnaces; Repeat above step 5 time, obtain the Zn of the about 400nm of thickness
0.99mn
0.01te
0.99o
0.01semiconductor film material, then this thin-film material normal temperature is deposited two days, 400 ℃ of Muffle furnaces are annealed 1 hour, finally obtain Zn
0.99mn
0.01te
0.99o
0.01film.
detect embodiment
The Zn exemplarily making with embodiment 2 below
0.97mn
0.03te
0.97o
0.03film is that example is analyzed membrane configuration of surface, X-ray diffraction and absorption spectrum situation in the middle of zinc-manganese tellurium oxygen of the present invention, and analysis result is as shown in accompanying drawing 1 to 3.It will be appreciated by those skilled in the art that every all zinc-manganese tellurium oxygen Intermediate Gray films within the scope of the present invention all have same or analogous following performance.
Wherein, the test method of above-mentioned analysis is standard method of analysis known in the art, and:
Fig. 1 is for adopting the AFM model A100-SGS of Beijing, Beijing Electronics Co., Ltd. to carry out the resulting atomic force microscope picture of atomic force microscope surface analysis;
Fig. 2 is for adopting the XRD model 6100 of Shimadzu business administration (China) Co., Ltd to carry out the resulting collection of illustrative plates of X-ray diffraction spectrum;
Fig. 3 is for adopting SPECORD250PLUS (UVVIS) ultraviolet-uisible spectrophotometer of Analytik Jena AG to carry out the resulting absorption factor collection of illustrative plates of absorption spectroanalysis.
From Fig. 1 to 3, zinc-manganese tellurium oxygen Intermediate Gray film surface of the present invention is smooth smooth, the polycrystalline state with good properties of crystal lattice, compare the optical absorption characteristics of parent semiconductor ZnTe, obviously widened the absorption bands of light, there is good absorbing properties, can directly predict that it has potential broad prospect of application in high performance solar batteries of future generation field.
Although the present invention is described in detail; but should be appreciated that foregoing description is not in order to limit the present invention, without departing from the spirit and scope of the present invention; any modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (9)
1. a preparation method for zinc-manganese tellurium oxygen colloidal sol, described zinc-manganese tellurium oxygen colloidal sol is Zn
1-ymn
yte
1-xo
xcolloidal sol, wherein, 0 < x < 1,0 < y < 1, is characterized in that, described preparation method comprises the following steps:
(1) under inert gas, in tellurium powder, add tri octyl phosphine solution, seal ultrasonic processing 45 minutes～60 minutes, obtain tellurium tri octyl phosphine solution, be designated as solution I; Wherein, the mol ratio of described tellurium powder and tri octyl phosphine solution is 1:45～1:90, and the molar concentration of tri octyl phosphine solution is 25mmol/L～50mmol/L;
(2) Mn (CH that is 6:520～30:540 by mass ratio
3cOO)
24H
2o powder and Zn (CH
3cOO)
22H
2o powder mixes, stabilizer, dispersant, chelating agent, crosslinking agent and deionized water that interpolation volume ratio is 1:3:1:1:5, and magnetic agitation, dissolving, then drip ammoniacal liquor and regulate pH value to 7.3～7.7, and the solution that obtains mixing, is designated as solution II;
(3) Zn (NO that to add with described mixeding liquid volume in the solution I that is 1:1 to volume ratio and the mixed liquor of II be 0.025mol/L than the molar concentration that is 1～3:22～24
3)
2, at 230～250 ℃, react 1～1.5 hour, obtain described zinc-manganese tellurium oxygen colloidal sol.
2. preparation method according to claim 1, is characterized in that, described stabilizer is diethanol amine, and described dispersant is absolute ethyl alcohol, and described chelating agent is citric acid, and described crosslinking agent is PEG6000.
3. the zinc-manganese tellurium oxygen colloidal sol that as claimed in claim 1 or 2 prepared by the method application in zinc-manganese tellurium oxygen Intermediate Gray film.
4. the zinc-manganese tellurium oxygen colloidal sol that as claimed in claim 1 or 2 prepared by the method application in solar cell.
5. a membrane preparation method in the middle of zinc-manganese tellurium oxygen, described zinc-manganese tellurium oxygen Intermediate Gray film is Zn
1-ymn
yte
1-xo
xintermediate Gray film, wherein, 0 < x < 1,0 < y < 1, is characterized in that, described preparation method comprises the following steps:
(1) substrate base is carried out to preliminary treatment, dry rear standby;
(2) zinc-manganese tellurium oxygen colloidal sol is coated in to the substrate base of processing through step (1), described coating speed is 4500～5000 revs/min; Wherein, described zinc-manganese tellurium oxygen colloidal sol is to adopt the preparation method described in claim 1 or 2 to prepare;
(3) substrate base step (2) having been applied carries out infrared baking 30min, then heat treatment 15min at 300 ℃;
(4) repeat above-mentioned coating, infrared baking and heat treatment 5 times, obtain described zinc-manganese tellurium oxygen Intermediate Gray film.
6. preparation method according to claim 5, is characterized in that, preliminary treatment described in step (1) comprises substrate base is adopted to liquid detergent, deionized water, absolute ethyl alcohol and deionized water ultrasonic cleaning successively.
7. according to the preparation method described in claim 5 or 6, it is characterized in that, described substrate base is that purity is more than 99.9999% monocrystalline silicon piece.
8. according to the preparation method described in claim 5 or 6, it is characterized in that, described preparation method also comprises: the zinc-manganese tellurium oxygen Intermediate Gray film normal temperature making in step (4) is deposited 48 hours, then at 400 ℃, annealed 1 hour.
9. the application of the zinc-manganese tellurium oxygen Intermediate Gray film that prepared by the method as described in any one in claim 5 to 8 in solar cell.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048877A (en) * | 2004-10-26 | 2007-10-03 | 巴斯福股份公司 | Photovoltaic cell comprising a photovoltaically active semiconductor material |
| CN102939668A (en) * | 2010-04-21 | 2013-02-20 | 安可太阳能股份有限公司 | Method of fabricating solar cells with electrodeposited compound interface layers |
-
2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048877A (en) * | 2004-10-26 | 2007-10-03 | 巴斯福股份公司 | Photovoltaic cell comprising a photovoltaically active semiconductor material |
| CN102939668A (en) * | 2010-04-21 | 2013-02-20 | 安可太阳能股份有限公司 | Method of fabricating solar cells with electrodeposited compound interface layers |
Non-Patent Citations (2)
| Title |
|---|
| A. AVDONIN,ET AL.: "Preparation and Optical Properties of Zn1¡xMnxTe1¡yOy Highly Mismatched Alloy", 《ACTA PHYSICA POLONICA A》 * |
| A. AVDONIN,ET AL.: "Preparation and Optical Properties of Zn1¡xMnxTe1¡yOy Highly Mismatched Alloy", 《ACTA PHYSICA POLONICA A》, vol. 112, no. 2, 31 December 2007 (2007-12-31) * |
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