CN103560156B - A kind of zinc-manganese tellurium oxygen colloidal sol, middle membrane preparation method and application thereof - Google Patents
A kind of zinc-manganese tellurium oxygen colloidal sol, middle membrane preparation method and application thereof Download PDFInfo
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- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 36
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001301 oxygen Substances 0.000 title claims abstract description 36
- 239000012528 membrane Substances 0.000 title claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 13
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 239000007788 liquid 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
- 239000003599 detergent Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- QERYCTSHXKAMIS-UHFFFAOYSA-M thiophene-2-carboxylate Chemical compound [O-]C(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-M 0.000 claims 1
- 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
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 229940123150 Chelating agent Drugs 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 229910007709 ZnTe Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 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
- 238000001228 spectrum Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 230000003287 optical effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910017231 MnTe Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000005611 electricity Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VMINMXIEZOMBRH-UHFFFAOYSA-N manganese(ii) telluride Chemical compound [Te]=[Mn] VMINMXIEZOMBRH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
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 present invention relates to a kind of zinc-manganese tellurium oxygen colloidal sol, middle membrane preparation method and application thereof, be specially: adopt K cryogenic treatment method, with Mn (CH3COO)2·4H2O and Zn (CH3COO)2·2H2O is raw material, adds stabilizing agent, dispersant, chelating agent, crosslinking agent and deionized water, and magnetic agitation is fully dissolved, and mixes with tellurium tri octyl phosphine solution, drips ammoniacal liquor and regulates after pH value, splashes into Zn (NO3)2Solution mixes, reaction at 240 DEG C, the cooling colloidal sol that obtains; Again gained colloidal sol is dripped on cleaned in advance monocrystalline silicon piece, evenly applies, infrared heating, then through the heat treatment of 300 DEG C, repeat to drip, apply, heating repeatedly forms film, last, by this film at 400 DEG C annealing in process to improve surface property. The collosol and gel that the present invention adopts is in conjunction with spin coated technology, and technique is simple, temperature lower (approximately 250 DEG C), be suitable for large area and produce.
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(Zn1-yMnyTe1-xOx) preparation method of colloidal sol, the zinc-manganese tellurium oxygen taking this colloidal sol as raw material(Zn1-yMnyTe1-xOx) 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, the abundant solar energy but utilization is cheapGenerating is still difficult to realize at present, is because the cost of solar cell is too expensive, on the other hand on the one handLower to the utilization ratio of solar energy. At present, fully absorb sunshine and improve efficiency of solar cellA kind of important method is to adopt many knot laminated construction, and way is by two or more sons different band gap conventionallyBattery is cascaded successively by band gap size. Its essence is equivalent to solar spectrum to be divided into several sections, eachSub-battery absorbs and immediate that section of light of its band gap. So both increased the absorption to low energy end spectrumRate, has reduced again the energy loss of high-energy photons, and the advantage that improves battery efficiency is clearly.But in actual process, between each sub-battery, run into a series of problem: current-unbalance, interfaceExist 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 sunshine fully absorbs, and is that Intermediate Gray is efficientThe most important part of solar cell. In the time that illumination is mapped to Intermediate Gray semi-conducting material, Electron absorptionAn energy is higher than band gap EgPhoton directly transit to conduction band from valence band, also can absorb respectively two energyAmount is lower than band gap EgPhoton enter again conduction band via Intermediate Gray from valence band. Visible Intermediate Gray has played electricityThe springboard effect of son from valence band to conduction band, can increase the absorption of material to long-wave band photon. Manufacture Intermediate GraySolar battery structure is simple, only need to intermediate zone material be clipped in traditional p-type and N-shaped semiconductor itBetween, itself and electrode are separated, be extracted to n district at electronics from conduction band like this, hole is extracted from valence bandDuring to p district, carrier can not be collected by Intermediate Gray. Therefore, Intermediate Gray is improving battery short circuit electricityWhen stream, can not reduce open-circuit voltage, open-circuit voltage is still determined by the band gap of material of main part. Due to centreBand solar cell can utilize sunshine efficiently, and the conversion efficiency of single-unit Intermediate Gray solar cell and more piece passThe transformation efficiency of system pn knot series connection solar cell is suitable.
Although Intermediate Gray solar cell has outstanding advantage utilizing aspect solar energy, suitable inBetween carrying material still among research and discovery. It is mainly the base that need to solve due to Intermediate Gray solar cellIn this problem, most critical be efficient absorption and the conversion of light, therefore efficient Intermediate Gray solar cell pairIntermediate zone material has harsh requirement, for example: in order to make electronics be smoothly through Intermediate Gray transition, centreBand should be that part is filled up and isolated being present among host's semiconductor band gap; In addition, to Intermediate GrayAbsorption coefficient of light of level of energy in host's semiconductor and respectively energy band-to-band transition etc. and Intermediate GrayRelevant physical characteristic has strict requirement.
High mismatch alloy is a kind of new material, substituted element and be substituted the electricity that between element, existence is largerNegativity difference. As in III-V compound, the nitrogen element that group Ⅴ element is partly diluted replaces, orPerson is in II-VI compound, and the oxygen element that VI family element is partly diluted replaces, and forms high mismatchAlloy. Replace atom and be substituted electronegativity difference larger between atom and cause its uncommon can knot by bandStructure can be explained with anti-cross band model. According to this model, the local state that N or O are relevant and hostThe expansion state of semi-conducting material interacts, and determines the Energy band electron structure of high mismatch alloy. Anti-cross energyBand model prophesy: if localized state energy level just lower than conduction band edge, just has arrowband shape in forbidden bandBecome. The people such as the K.M.Yu of Univ California-Berkeley as far back as 2002～2003 years based on being with anti-crossModel (bandanticrossing, BAC), the method by laser molecular beam epitaxy by O introduce ZnTe,MnTe and Zn1-yMnyTe part substitute Te wherein, form high mismatch alloy intermediate zone material,II-O-VI family semi-conducting material is carried out to early-stage Study, for electronegativity difference causes Intermediate Gray and then promotes lightEffective absorption lay a good foundation.
At Zn1-yMnyTe1-xOxIn middle membrane preparation, mainly contain at present following several method: swashOptical molecule beam epitaxy technology (MBE), metal organic vapor phase epitaxy method (MOCVD), microwave magnetic control spattersShooting method and pulsed laser deposition technology and spraying high temperature pyrolysis etc. But these method complex process, becomeThis is higher, and to equipment requirement harshness.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of technique simple, with low cost,Be applicable to zinc-manganese tellurium oxygen colloidal sol and the middle membrane preparation method of zinc-manganese tellurium oxygen of suitability for industrialized production and be somebody's turn to doColloidal 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 solFor Zn1-yMnyTe1-xOxColloidal sol, wherein, 0 < x < 1,0 < y < 1, described preparation method comprises followingStep:
(1) under inert gas, in tellurium powder, add tri octyl phosphine solution, seal 45 points of ultrasonic processingClock～60 minute, obtain tellurium tri octyl phosphine solution, are designated as solution I; Wherein, described tellurium powder and three pungentThe mol ratio of base 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 ratio3COO)2·4H2O powder andZn(CH3COO)2·2H2O powder mixes, to add volume ratio be 1:3:1:1:5 stabilizing agent, dispersant,Chelating agent, crosslinking agent and deionized water, magnetic agitation, dissolving, then drip ammoniacal liquor and regulate pH value extremely7.3～7.7, the solution that obtains mixing, is designated as solution II; In this step, the meter of quality and volumeAmount unit can be mg and mL, for example Mn (CH3COO)2·4H2O powder 6～30mg,Zn(CH3COO)2·2H2O powder 520～540mg, stabilizing agent is 5mL, dispersant 15mL, chelatingAgent 5mL, crosslinking agent 5mL and deionized water 25mL;
(3) in the solution I that is 1:1 to volume ratio and the mixed liquor of II, add and described mixeding liquid volume ratioZn (the NO that the molar concentration that is 1～3:22～24 is 0.5mol/L3)2, at 240 DEG C, react 1～1.5 hours, obtain described zinc-manganese tellurium oxygen colloidal sol.
In above-mentioned preparation method, described stabilizing agent is diethanol amine, and described dispersant is absolute ethyl alcohol,Described chelating agent is citric acid, and described crosslinking agent is PEG6000.
On the other hand, the present invention also provides a kind of as prepared by above-mentioned preparation method zinc-manganese tellurium oxygen colloidal sol at zincApplication in manganese tellurium oxygen Intermediate Gray film.
Another aspect, the present invention also provides zinc-manganese tellurium oxygen colloidal sol prepared by a kind of as above-mentioned preparation method tooApplication in sun energy battery.
Again on the one hand, the present invention also provides a kind of zinc-manganese tellurium oxygen middle membrane preparation method, described zincManganese tellurium oxygen Intermediate Gray film is Zn1-yMnyTe1-xOxIntermediate Gray film, wherein, 0 < x < 1,0 < y < 1,Described preparation method comprises the following steps:
(1) substrate base is carried out to pretreatment, dry rear for subsequent use;
(2) zinc-manganese tellurium oxygen colloidal sol is coated in to the substrate base of processing through step (1), described coatingSpeed is 4500～5000 revs/min; Wherein, described zinc-manganese tellurium oxygen colloidal sol be adopt claim 1 orPrepared by the preparation method described in 2;
(3) substrate base step (2) having been applied carries out infrared baking 30min, then existsHeat treatment 15min at 300 DEG C;
(4) repeat above-mentioned coating, infrared baking and heat treatment 5 times, obtain in the middle of described zinc-manganese tellurium oxygenBand film.
In above-mentioned preparation method, pretreatment described in step (1) comprises substrate base is adopted successivelyLiquid detergent, deionized water, absolute ethyl alcohol and deionized water ultrasonic cleaning.
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: by the zinc-manganese making in step (4)Tellurium oxygen Intermediate Gray film normal temperature is deposited 48 hours, then at 300 DEG C, anneals 1 hour.
Finally, the invention provides zinc-manganese tellurium oxygen Intermediate Gray film prepared by a kind of as above-mentioned preparation method tooApplication in sun energy battery.
The present invention does not limit the preparation method of described zinc-manganese tellurium oxygen Intermediate Gray film for solar cell,It will be appreciated by those skilled in the art that every can be by zinc-manganese tellurium oxygen Intermediate Gray film for solar cellPreparation method all can be used for the present invention.
Compared with prior art, the present invention at least has following beneficial effect: the colloidal sol that the present invention adoptsGel is in conjunction with spin coated technology, and technique is simple, temperature lower (approximately 250 DEG C), be suitable for large areaProduce, and the Zn of preparation1-yMnyTe1-xOxIntermediate Gray thin-film material surface is smooth, has betterThe polycrystalline state of properties of crystal lattice, compare the optical absorption characteristics of parent semiconductor ZnTe, obviously widened lightAbsorption bands, there is good absorbing properties, have potential in efficient solar battery of future generation fieldApplication prospect.
Brief description of the drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the AFM 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.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail the embodiment providingOnly in order to illustrate the present invention, instead of in order to limit the scope of the invention.
Embodiment 1
1.Zn0.95Mn0.05Te0.95O0.05The 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 50mLMolar concentration is the tri octyl phosphine solution of 25mmol/L, obtains tellurium tri octyl phosphine (TOPTe) evenly moltenLiquid, is designated as solution I;
(b) accurately take the Mn (CH of 30mg by stoichiometric proportion3COO)2·4H2O, 520mg'sZn(CH3COO)2·2H2The lemon of the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, 5mLThe PEG6000 of acid and 5mL puts into beaker, and mixes with the deionized water of 25mL, and magnetic force stirsMix abundant dissolving, slowly drip ammoniacal liquor (NH3·H2O), the pH value of regulator solution is 7.3 to be alkalescent,After mixing, obtain solution II;
(c) then, the cooling solution II of 22mL is mixed with 22mL cooling solution I, drip 6mLConcentration is the Zn (NO of 0.025mol/L3)2, pack in the 50mL reactor of heat resisting and pressure resisting, control temperatureSpend approximately 240 DEG C, the cooling colloidal sol that obtains after 60 minutes.
2.Zn0.95Mn0.05Te0.95O0.05Middle membrane preparation
(a) pretreatment of substrate base: be by the purity that is of a size of 30mm × 50mm × 1mmMore than 99.9999% monocrystalline silicon piece cleans after several times with liquid detergent, adopts successively deionized water, anhydrous secondAlcohol, deionized water ultrasonic cleaning, dry up for subsequent use by the deionized water on glass substrate with hair-dryer;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with 4500Rev/min speed be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, soAfter heat treatment 15 minutes in 300 DEG C of Muffle furnaces; Repeat above dropping, coating, baking and heat treatmentStep 5 time, the Zn of the about 400nm of acquisition thickness0.95Mn0.05Te0.95O0.05Semiconductor film material, thenThis thin-film material normal temperature is deposited two days, and 400 DEG C of Muffle furnaces are annealed 1 hour, finally obtainZn0.95Mn0.05Te0.95O0.05Film.
Embodiment 2
1.Zn0.97Mn0.03Te0.97O0.03The 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 50mLMolar concentration is the tri octyl phosphine solution of 30mmol/L, obtains tellurium tri octyl phosphine (TOPTe) evenly moltenLiquid, is designated as solution I;
(b) accurately take the Mn (CH of 18mg by stoichiometric proportion3COO)2·4H2O, 530mg'sZn(CH3COO)2·2H2The lemon of the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, 5mLThe PEG6000 of acid and 5mL puts into beaker, and mixes with the deionized water of 25mL, and magnetic force stirsMix abundant dissolving, slowly drip ammoniacal liquor (NH3·H2O), the pH value of regulator solution is 7.4 to be alkalescent,After mixing, obtain solution II;
(c) then, the cooling solution II of 23mL is mixed with 23mL cooling solution I, drip 4mLConcentration is the Zn (NO of 0.025mol/L3)2, pack in the 50mL reactor of heat resisting and pressure resisting, control temperatureSpend approximately 240 DEG C, the cooling colloidal sol that obtains after 90 minutes.
2.Zn0.97Mn0.03Te0.97O0.03Middle membrane preparation
(a) pretreatment of substrate base: be by the purity that is of a size of 30mm × 50mm × 1mmMore than 99.9999% monocrystalline silicon piece cleans after several times with liquid detergent, adopts successively deionized water, anhydrous secondAlcohol, deionized water ultrasonic cleaning, dry up for subsequent use by the deionized water on glass substrate with hair-dryer;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with 4800Rev/min speed be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, soAfter heat treatment 15 minutes in 300 DEG C of Muffle furnaces; Repeat above dropping, coating, baking and heat treatmentStep 5 time, the Zn of the about 400nm of acquisition thickness0.97Mn0.03Te0.97O0.03Semiconductor film material, thenThis thin-film material normal temperature is deposited two days, and 400 DEG C of Muffle furnaces are annealed 1 hour, finally obtainZn0.97Mn0.03Te0.97O0.03Film.
Embodiment 3
1.Zn0.99Mn0.01Te0.99O0.01The 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 50mLMolar concentration is the tri octyl phosphine solution of 50mmol/L, obtains tellurium tri octyl phosphine (TOPTe) evenly moltenLiquid, is designated as solution I;
(b) accurately take the Mn (CH of 6mg by stoichiometric proportion3COO)2·4H2O, 540mg'sZn(CH3COO)2·2H2The lemon of the diethanol amine of O and 5mL, the absolute ethyl alcohol of 15mL, 5mLThe PEG6000 of acid and 5mL puts into beaker, and mixes with the deionized water of 25mL, and magnetic force stirsMix abundant dissolving, slowly drip ammoniacal liquor (NH3·H2O), the pH value of regulator solution is 7.5 to be alkalescent,After mixing, obtain solution II;
(c) then, the cooling solution II of 24mL is mixed with 24mL cooling solution I, drip 2mLConcentration is the Zn (NO of 0.025mol/L3)2, pack in the 50mL reactor of heat resisting and pressure resisting, control temperatureSpend approximately 250 DEG C, the cooling colloidal sol that obtains after 90 minutes.
2.Zn0.99Mn0.01Te0.99O0.01Middle membrane preparation
(a) pretreatment of substrate base: be by the purity that is of a size of 30mm × 50mm × 1mmMore than 99.9999% monocrystalline silicon piece cleans after several times with liquid detergent, adopts successively deionized water, anhydrous secondAlcohol, deionized water ultrasonic cleaning, dry up for subsequent use by the deionized water on glass substrate with hair-dryer;
(b) on cleaned in advance Si sheet, drip the above-mentioned colloidal solution having prepared, with 5000Rev/min speed be evenly coated on Si sheet, film is placed under infrared lamp and is toasted 30 minutes, soAfter heat treatment 15 minutes in 300 DEG C of Muffle furnaces; Repeat above step 5 time, obtain the about 400nm of thicknessZn0.99Mn0.01Te0.99O0.01Semiconductor film material, then this thin-film material normal temperature is deposited two days,400 DEG C of Muffle furnaces are annealed 1 hour, finally obtain Zn0.99Mn0.01Te0.99O0.01Film.
Detect embodiment
The Zn exemplarily making with embodiment 2 below0.97Mn0.03Te0.97O0.03Film is that example is come thisIn the middle of bright zinc-manganese tellurium oxygen, membrane configuration of surface, X-ray diffraction and absorption spectrum situation are dividedAnalyse, analysis result is as shown in accompanying drawing 1 to 3. It will be appreciated by those skilled in the art that every in the present inventionAll zinc-manganese tellurium oxygen Intermediate Gray films in scope 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 adopts the AFM model A100-SGS of Beijing, Beijing Electronics Co., Ltd. to carry out atomic forceThe AFM picture that microscope surface analysis obtains;
Fig. 2 adopts the XRD model 6100 of Shimadzu business administration (China) Co., Ltd to carry out XThe collection of illustrative plates that ray diffraction spectra obtains;
Fig. 3 is the SPECORD250PLUS (UV that adopts Analytik Jena AGVIS) ultraviolet-uisible spectrophotometer carries out the absorption factor collection of illustrative plates that absorption spectroanalysis obtains.
From Fig. 1 to 3, zinc-manganese tellurium oxygen Intermediate Gray film surface of the present invention is smooth, hasThe polycrystalline state of good properties of crystal lattice, compares the optical absorption characteristics of parent semiconductor ZnTe, has obviously widenedThe absorption bands of light, has good absorbing properties, can directly predict that it is at high-efficiency solar of future generationField of batteries has potential broad prospect of application.
Although the present invention is described in detail, should be appreciated that foregoing description is not in order to limitThe present invention, without departing from the spirit and scope of the present invention, any amendment of doing, is equal to and replacesChange, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for zinc-manganese tellurium oxygen colloidal sol, described zinc-manganese tellurium oxygen colloidal sol is Zn1-yMnyTe1-xOxColloidal 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 45 points of ultrasonic processingClock～60 minute, obtain tellurium tri octyl phosphine solution, are designated as solution I; Wherein, described tellurium powder and three pungentThe mol ratio of base 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 ratio3COO)2·4H2O powder andZn(CH3COO)2·2H2O powder mixes, to add volume ratio be 1:3:1:1:5 stabilizing agent, dispersant,Chelating agent, crosslinking agent and deionized water, magnetic agitation, dissolving, then drip ammoniacal liquor and regulate pH value extremely7.3～7.7, the solution that obtains mixing, is designated as solution II, wherein, and Mn (CH3COO)2·4H2OPowder 6～30mg, Zn (CH3COO)2·2H2O powder 520～540mg, stabilizing agent is 5mL, dividesPowder 15mL, chelating agent 5mL, crosslinking agent 5mL and deionized water 25mL;
(3) in the solution I that is 1:1 to volume ratio and the mixed liquor of II, add and described mixeding liquid volume ratioZn (the NO that the molar concentration that is 1～3:22～24 is 0.025mol/L3)2, anti-at 230～250 DEG CAnswer 1～1.5 hour, obtain described zinc-manganese tellurium oxygen colloidal sol.
2. preparation method according to claim 1, is characterized in that, described stabilizing agent is diethanolAmine, 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 method is in the middle of zinc-manganese tellurium oxygenWith the application in film.
4. the zinc-manganese tellurium oxygen colloidal sol that as claimed in claim 1 or 2 prepared by method is in solar cellApplication.
5. a membrane preparation method in the middle of zinc-manganese tellurium oxygen, described zinc-manganese tellurium oxygen Intermediate Gray film isZn1-yMnyTe1-xOxIntermediate Gray film, wherein, 0 < x < 1,0 < y < 1, is characterized in that, described inPreparation method comprises the following steps:
(1) substrate base is carried out to pretreatment, dry rear for subsequent use;
(2) zinc-manganese tellurium oxygen colloidal sol is coated in to the substrate base of processing through step (1), described coatingSpeed is 4500～5000 revs/min; Wherein, described zinc-manganese tellurium oxygen colloidal sol be adopt claim 1 orPrepared by the preparation method described in 2;
(3) substrate base step (2) having been applied carries out infrared baking 30min, then existsHeat treatment 15min at 300 DEG C;
(4) repeat above-mentioned coating, infrared baking and heat treatment 5 times, obtain in the middle of described zinc-manganese tellurium oxygenBand film.
6. preparation method according to claim 5, is characterized in that, pre-described in step (1)Processing comprises and adopts successively liquid detergent, deionized water, absolute ethyl alcohol and deionized water ultrasonic substrate baseClean.
7. according to the preparation method described in claim 5 or 6, it is characterized in that described substrate baseFor 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 methodAlso comprise: the zinc-manganese tellurium oxygen Intermediate Gray film normal temperature making in step (4) is deposited 48 hours, thenAt 400 DEG C, anneal 1 hour.
9. a zinc-manganese tellurium oxygen Intermediate Gray prepared by the method as described in any one in claim 5 to 8The application of film in solar cell.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (1)
| Title |
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| Preparation and Optical Properties of Zn1¡xMnxTe1¡yOy Highly Mismatched Alloy;A. Avdonin,et al.;《ACTA PHYSICA POLONICA A》;20071231;第112卷(第2期);407-409 * |
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