CN104681280A - Preparation method of cadmium sulfide/ Co-doped cadmium selenide sensitizer for solar cell - Google Patents

Preparation method of cadmium sulfide/ Co-doped cadmium selenide sensitizer for solar cell Download PDF

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CN104681280A
CN104681280A CN201310634575.4A CN201310634575A CN104681280A CN 104681280 A CN104681280 A CN 104681280A CN 201310634575 A CN201310634575 A CN 201310634575A CN 104681280 A CN104681280 A CN 104681280A
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sensitizer
quantum
solar cell
cdse
quantum dot
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邹小平
何胜
滕功清
赵川
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Beijing Information Science and Technology University
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Beijing Information Science and Technology University
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Abstract

The invention relates to a preparation method of a cadmium sulfide/ Co-doped cadmium selenide sensitizer for a solar cell. The method comprises the following steps of doping Co impurity atoms into CdSe semiconductor quantum dots, and then co-sensitizing the CdSe semiconductor quantum dots and the CdS semiconductor quantum dots to form the sensitizer to assemble the quantum dot sensitization solar cell. Thransmission paths of charges inside the cell are optimized, so that electron holes can be more quickly separated, electrons can be more effectively injected into conduction bands of TiO2, dark current is reduced, and the short-circuit current, the open-circuit voltage and the photoelectric conversion efficiency of the solar cell are improved. The method is simple and easy to operate and low in cost, and can be used for large-area manufacturing.

Description

For the cadmium sulfide/cobalt doped cadmium selenide sensitizer preparation method of solar cell
Technical field
The invention belongs to technical field of solar, more specifically relate to a kind of cadmium sulfide for solar cell/cobalt doped cadmium selenide sensitizer preparation method.
Background technology
Along with developing rapidly of global economy, the sustainable growth of population and the dependence of the mankind to the energy are deepened gradually, and energy crisis and problem of environmental pollution have become the matter of utmost importance of 21 century facing mankind.In the face of the worldwide petrochemical energy is day by day exhausted, inexhaustible solar energy is undoubtedly the first-selection of human future energy development.Therefore, gazed at most using solar energy as new forms of energy source of supply, from technical development process or following perspectively all receive the close concern of all circles.The device being directly electric energy light energy conversion by photoelectric effect is exactly solar cell.In all kinds of novel solar battery, DSSC (DSSCs) with low cost, manufacture craft simply, relatively high photoelectric conversion efficiency and become study hotspot (O'Regan, B., , M., Nature, 1991,353,737).DSSCs will adsorb the wide bandgap semiconductor nano-crystal film of dyestuff as positive pole, the electro-conductive glass that surface is coated with one deck platinum as to electrode, positive pole and oxidationreduction electrolyte formed to adding between electrode.Dye molecule absorbs solar energy, and electronics is from ground state transition to excitation state, and the electronics above excitation state injects the TiO of next-door neighbour fast 2conduction band, the electronics lost in dyestuff is very fast to be compensated from electrolyte, enters TiO 2electronics in conduction band finally enters conducting film, then produces photoelectric current by external circuit to electrode.But, the stability of dyestuff need further raising, and price is also relatively high, so adopt low-cost low energy gap inorganic semiconductor quantum dot as sensitizer, the cost of battery can be reduced, improve stability, this battery is called quantum dot sensitized solar cell (QDSSCs).General dye absorber photon produces at most an electronics, and quantum dot can produce multiple electronics by a high-energy photon, greatly improves quantum yield (Nozik, A.J., Physica E, 2002,14,115).
But utilize quantum dot sensitized solar cell QDSSCs at present, its aggregate performance is also lower than DSSCs.In order to improve the photoelectric conversion efficiency of QDSSCs, extensively carry out the modification work to QDSSCs, wherein adulterating to quantum dot is also a kind of conventional effective ways, CN102163502A discloses a kind of method being doped with Ca foreign ion in CdS quantum dot, improve the conduction band of CdS, improve the absorption situation of CdS quantum dot in electrode material surface, inhibit the generation of dark current, improve short circuit current and the photoelectric conversion efficiency of solar cell.CN102760580A discloses a kind of Co doping CdSe quantum dot sensitization TiO 2the method of nanometer rods optoelectronic pole.Utilize the method for electrochemical deposition at TiO 2monocrystal nano rod array completes the deposition of Co doping CdSe quantum dot.The incorporation of Co ion is 1% ~ 4% (percentage by weight), Co can regulate its band gap on the one hand to the doping of CdSe, make its influx and translocation in visible-range, absorption region is widened, and then improve light utilization efficiency, the doping of Co can increase its carrier concentration on the other hand, improves the transmission rate of electronics, increase the efficiency that electrode collects electronics, thus improve density of photocurrent.The people such as the Liu Yan of Jilin Institute of Chemical Technology pass through microwave irradiation technology, by transition metal Co 2+successfully be doped to the inside of CdS quantum dot.Ultraviolet absorption peak and the fluorescence emission peak of the quantum dot after doping all correspondingly there occurs red shift.The emission peak scope of fluorescence spectrum has widened 50nm, and fluorescent stability and chemical stability are greatly improved.In addition, (Pralay K.Santra, J.Am.Chem.Soc.2012,134,2508-2511) by SILAR method by Mn 2+be incorporated in CdS quantum dot, make electronics more effectively can be injected into TiO 2in, improve the short circuit current of solar cell, open circuit voltage and photoelectric conversion efficiency.(Jin-Wook Lee, SCIENTIFIC REPORTS|3:1050|DOI:10.1038/srep01050) by SILAR method by Hg 2+be doped in PbS quantum, enhance electron injection, inhibit charge recombination, current density is doubled, and battery efficiency reaches 5.6%.But to be adulterated Co to CdSe quantum dot by SILAR method at present, the adulterate work of CdSe sensitization solar battery of preparation CdS/Co have not been reported.
Summary of the invention
In order to solve the problem, the invention provides a kind of CdS/Co for solar cell doping CdSe sensitizer preparation method, improve the photoelectric characteristic of CdSe semiconductor-quantum-point with this, improve the conduction band of CdSe semiconductor-quantum-point, make electronics more effectively can be injected into TiO 2in, decrease the complex centre of inside battery, electron hole more fast and effeciently can be separated, reduce dark current, and then improve the short circuit current of solar cell, open circuit voltage and photoelectric conversion efficiency.
The present invention implements by the following technical programs:
For the cadmium sulfide/cobalt doped CdSe quantum dots sensitizer preparation method of solar cell, the method is by Co 2+be doped to CdSe quantum dot, be total to sensitization with CdS quantum dot and be assembled into quantum dot sensitized solar cell as sensitizer.
The concrete steps of described method are:
1) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point cation Cd 2+soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
2) soluble salt solutions containing Co foreign atom being added step 1) in the cationic solution that is equipped with, wherein foreign atom is 1: 1-1: 1000 with the ratio of semiconductor-quantum-point molar concentration;
3) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point anion S 2-soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
4) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point anion Se 2-soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
5) will treat that the wide bandgap semiconductor light anode material of sensitization immerses step 1) 1-10min in the solution prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
6) by step 5) the light anode material that obtains immerses step 3) 1-10min in the anion solutions prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
7) by step 6) the light anode material that obtains immerses step 2) 1-10min in the cationic solution prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
8) by step 7) the light anode material that obtains immerses step 4) 1-60min in the anion solutions prepared, taking-up coordinative solvent is rinsed well, and dry up with nitrogen, then on light anode material, form CdS quantum dot and Co to adulterate CdSe quantum dot sensitization oxidant layer altogether.
The invention has the advantages that: be the Co of 1: 200 at this with Co, CdSe molar concentration rate 2+being doped to CdSe semiconductor-quantum-point is that example illustrates.CdS quantum dot is total to sensitization with the CdSe quantum dot of mixing Co and is assembled into quantum dot sensitized solar cell as sensitizer.By optimizing the transmission path of inside battery electric charge, improve the conduction band of CdSe quantum dot, electron hole can be separated more fast, and electronics is more effective is injected into TiO 2conduction band in, reduce dark current, improve the short circuit current of solar cell, open circuit voltage and photoelectric conversion efficiency.At 100mW/cm 2light-intensity conditions under, the short-circuit current density of this solar cell is 5.04mA/cm 2, open circuit voltage is 0.39V, and photoelectric conversion efficiency is 0.53%.The short-circuit current density of the quantum dot sensitized solar cell of unadulterated CdS/CdSe is 4.69mA/cm 2, open circuit voltage is 0.38V, photoelectric conversion efficiency 0.38%.After carrying out Co doping CdSe, short-circuit current density improves 7%, and open circuit voltage improves 2%, and photoelectric conversion efficiency improves 39%.
The present invention will be illustrated by example below, but the present invention is not limited to embodiment as described herein, and embodiments of the invention are only for setting forth the present invention further.That carries out content of the present invention for those skilled in the art substitutes, changes or changes, and these equivalent form of values fall in the application's limited range equally.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of CdS/Co doping CdSe light anode and unadulterated CdS/CdSe light anode; Wherein, A curve corresponds to the ultraviolet-visible absorption spectroscopy of unadulterated CdS/CdSe light anode, and B curve corresponds to the ultraviolet-visible absorption spectroscopy of CdS/Co doping CdSe light anode;
Fig. 2 is the J-V curve of CdS/Co doping CdSe and the quantum dot sensitized solar cell of unadulterated CdS/CdSe; Wherein, C corresponds to the quantum dot sensitized solar cell of unadulterated CdS/CdSe, and D corresponds to CdS/Co doping CdSe quantum dot sensitization solar battery;
Fig. 3 is the performance parameter of CdS/Co doping CdSe and the quantum dot sensitized solar cell of unadulterated CdS/CdSe;
Fig. 4 is the electricity conversion curve of CdS/Co doping CdSe and the quantum dot sensitized solar cell of unadulterated CdS/CdSe; Wherein, E corresponds to the quantum dot sensitized solar cell of unadulterated CdS/CdSe, and F corresponds to CdS/Co doping CdSe quantum dot sensitization solar battery;
Fig. 5 is the electrochemical alternate impedance spectrum of CdS/Co doping CdSe and the quantum dot sensitized solar cell of unadulterated CdS/CdSe; Wherein, G corresponds to the quantum dot sensitized solar cell of unadulterated CdS/CdSe, and H corresponds to CdS/Co doping CdSe quantum dot sensitization solar battery, and illustration is the equivalent electric circuit of electrochemical alternate impedance spectrum;
Fig. 6 is the parameter of the quantum dot sensitized solar cell electrochemical alternate impedance spectrum of CdS/Co doping CdSe and unadulterated CdS/CdSe.
Embodiment
Cadmium sulfide/cobalt doped CdSe quantum dots sensitization solar battery and preparation method thereof, the method is by Co 2+be doped to CdSe quantum dot, then be assembled into quantum dot sensitized solar cell with the common sensitization of CdS quantum dot as sensitizer.
Embodiment 1
The concrete steps of cadmium sulfide/cobalt doped CdSe quantum dots sensitizer preparation method are:
1) Cd (NO that concentration is 0.1M is equipped with 3) 2solution and Na 2s solution, puts into the water-bath 30-60min of 20-50 DEG C;
2) by C 4h 6coO 44H 2o adds step 1) Cd (NO that is equipped with 3) 2in the middle of solution, wherein Co 2+with Cd 2+molar concentration rate be 1: 1;
3) by step 2) solution of gained puts into the water-bath 30min of 30 DEG C;
4) the light anode material TiO of sensitization will be treated 2immerse step 1) Cd (NO for preparing 3) 25min in solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
5) by step 4) the light anode material that obtains immerses step 1) Na for preparing 25min in S solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
6) by step 5) the light anode material that obtains immerses step 3) 5min in the solution prepared, taking-up coordinative solvent cleans up, and dries up with nitrogen;
7) by step 6) the light anode material that obtains immerses Na prepared by circumfluence method 2seSO 3concentration (is the Na of 0.12M by solution 2sO 3, 0.06M Se powder, then add a small amount of artificial zeolite, dissolve in deionized water.With reflow method, 70 DEG C, carry out 7h under water bath condition.Finally filter, remove unreacted Se powder and artificial zeolite) in, at 50 DEG C of Water Under bath 30min, taking-up coordinative solvent cleans up, and dries up with nitrogen, then on light anode material, define CdS/Co mix CdSe semiconductor-quantum-point sensitization oxidant layer.
Embodiment 2
The concrete steps of cadmium sulfide/cobalt doped CdSe quantum dots sensitizer preparation method are:
1) Cd (NO that concentration is 0.1M is equipped with 3) 2solution and Na 2s solution, puts into the water-bath 30-60min of 20-50 DEG C;
2) by C 4h 6coO 44H 2o adds step 1) Cd (NO that is equipped with 3) 2in the middle of solution, wherein Co 2+with Cd 2+molar concentration rate be 1: 500;
3) by step 2) solution of gained puts into the water-bath 30min of 30 DEG C;
4) the light anode material TiO of sensitization will be treated 2immerse step 1) Cd (NO for preparing 3) 25min in solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
5) by step 4) the light anode material that obtains immerses step 1) Na for preparing 25min in S solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
6) by step 5) the light anode material that obtains immerses step 3) 5min in the solution prepared, taking-up coordinative solvent cleans up, and dries up with nitrogen;
7) by step 6) the light anode material that obtains immerses Na prepared by circumfluence method 2seSO 3concentration (is the Na of 0.12M by solution 2sO 3, 0.06M Se powder, then add a small amount of artificial zeolite, dissolve in deionized water.With reflow method, 70 DEG C, carry out 7h under water bath condition.Finally filter, remove unreacted Se powder and artificial zeolite) in, at 50 DEG C of Water Under bath 30min, taking-up coordinative solvent cleans up, and dries up with nitrogen, then on light anode material, define CdS/Co mix CdSe semiconductor-quantum-point sensitization oxidant layer.
Embodiment 3
The concrete steps of cadmium sulfide/cobalt doped CdSe quantum dots sensitizer preparation method are:
1) Cd (NO that concentration is 0.1M is equipped with 3) 2solution and Na 2s solution, puts into the water-bath 30-60min of 20-50 DEG C;
2) by C 4h 6coO 44H 2o adds step 1) Cd (NO that is equipped with 3) 2in the middle of solution, wherein Co 2+with Cd 2+molar concentration rate be 1: 1000;
3) by step 2) solution of gained puts into the water-bath 30min of 30 DEG C;
4) the light anode material TiO of sensitization will be treated 2immerse step 1) Cd (NO for preparing 3) 25min in solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
5) by step 4) the light anode material that obtains immerses step 1) Na for preparing 25min in S solution, taking-up coordinative solvent cleans up, and dries up with nitrogen;
6) by step 5) the light anode material that obtains immerses step 3) 5min in the solution prepared, taking-up coordinative solvent cleans up, and dries up with nitrogen;
7) by step 6) the light anode material that obtains immerses Na prepared by circumfluence method 2seSO 3concentration (is 0.12M Na by solution 2sO 3, 0.06M Se powder dissolve in deionized water.With reflow method, 70 DEG C, carry out 7h under water bath condition.Finally filter, remove unreacted Se powder and artificial zeolite) in, at 50 DEG C of Water Under bath 30min, taking-up coordinative solvent cleans up, and dries up with nitrogen, then on light anode material, define CdS/Co mix CdSe semiconductor-quantum-point sensitization oxidant layer.

Claims (7)

1., for the cadmium sulfide/cobalt doped cadmium selenide sensitizer preparation method of solar cell, it is characterized in that described method is by dopant impurity atoms in semiconductor-quantum-point, be assembled into quantum dot sensitized solar cell as sensitizer.
2. cadmium sulfide according to claim 1/cobalt doped cadmium selenide sensitizer, is characterized in that described semiconductor-quantum-point is cadmium sulfide (CdS), cadmium selenide (CdSe).
3. cadmium sulfide according to claim 1/cobalt doped cadmium selenide sensitizer, is characterized in that described preparation method is successive ionic layer adsorption and reaction (Successive Ionic Layer Adsorption and Reaction, SILAR).
4. cadmium sulfide according to claim 1/cobalt doped cadmium selenide sensitizer, is characterized in that described foreign atom is cobalt (Co).
5. cadmium sulfide according to claim 1/cobalt doped cadmium selenide sensitizer, is characterized in that described Co foreign atom mixes the CdSe semiconductor-quantum-point that CdSe quantum dot forms CdS/Co doping.
6. solar cell according to claim 1, is characterized in that described CdS semiconductor-quantum-point is total to sensitization with the CdSe quantum dot of mixing Co and is assembled into quantum dot sensitized solar cell as sensitizer.
7. cadmium sulfide according to claim 1/cobalt doped cadmium selenide sensitizer, is characterized in that the concrete steps of described method are:
1) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point cation Cd 2+soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
2) soluble salt solutions containing Co foreign atom being added step 1) in the cationic solution that is equipped with, wherein foreign atom is 1: 1-1: 1000 with the ratio of semiconductor-quantum-point molar concentration;
3) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point anion S 2-soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
4) being equipped with concentration is that 0.01M-1M contains semiconductor-quantum-point anion Se 2-soluble salt solutions, put into the water-bath constant temperature 30-60min of 20-50 DEG C;
5) will treat that the wide bandgap semiconductor light anode material of sensitization immerses step 1) 1-10min in the solution prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
6) by step 5) the light anode material that obtains immerses step 3) 1-10min in the anion solutions prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
7) by step 6) the light anode material that obtains immerses step 2) 1-10min in the cationic solution prepared, taking-up coordinative solvent is rinsed well, and dries up with nitrogen;
8) by step 7) the light anode material that obtains immerses step 4) 1-60min in the anion solutions prepared, taking-up coordinative solvent is rinsed well, and dry up with nitrogen, then on light anode material, form CdS quantum dot and Co to adulterate CdSe quantum dot sensitization oxidant layer altogether.
CN201310634575.4A 2013-12-03 2013-12-03 Preparation method of cadmium sulfide/ Co-doped cadmium selenide sensitizer for solar cell Pending CN104681280A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080577A (en) * 2015-09-11 2015-11-25 中国科学技术大学 Cobalt di-selenide nanobelt assembling sphere and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080577A (en) * 2015-09-11 2015-11-25 中国科学技术大学 Cobalt di-selenide nanobelt assembling sphere and preparation method and application thereof
CN105080577B (en) * 2015-09-11 2017-07-25 中国科学技术大学 Two cobaltous selenide nanobelts assembling ball, its preparation method and its application

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Application publication date: 20150603