CN103451599A - Cadmium telluride/bismuth telluride integrated nano structure material with photo-thermal synergic electric generation and preparation method thereof - Google Patents
Cadmium telluride/bismuth telluride integrated nano structure material with photo-thermal synergic electric generation and preparation method thereof Download PDFInfo
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 title abstract description 5
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title abstract 5
- 230000002195 synergetic effect Effects 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000004544 sputter deposition Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 14
- 229910052714 tellurium Inorganic materials 0.000 claims description 14
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 10
- 230000033228 biological regulation Effects 0.000 claims description 8
- 238000009825 accumulation Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000010849 ion bombardment Methods 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000001228 spectrum Methods 0.000 abstract description 16
- 239000002073 nanorod Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005286 illumination Methods 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005676 thermoelectric effect Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a cadmium telluride/bismuth telluride integrated nano structure material with photo-thermal synergic electric generation. The preparation method comprises the following: depositing a cadmium telluride nanorod layer on a conducting surface of a conducting glass substrate, and depositing a tellurium-doped bismuth telluride layer on the surface of the cadmium telluride nanorod layer to constitute the cadmium telluride/bismuth telluride integrated nano structure material. The material can simultaneously convert light and heat in the solar spectrum into electric power, thereby implementing the effect of photo-thermal synergic utilization. The invention also discloses a preparation method of the cadmium telluride/bismuth telluride integrated nano structure material.
Description
Technical field
The present invention relates to have the collaborative cadmium telluride (CdTe) that the effect sends a telegraph/Tellurobismuthite (Bi that utilizes of photo-thermal
2te
3) integrated material and method for making thereof.
Background technology
Sun power is as the new forms of energy of cleanliness without any pollution, under the current background of vigorously advocating low-carbon economy, carrying the vital task that national energy-saving reduces discharging and is subject to everybody extensive concern.Solar spectrum energy 99% all concentrates on UV-light to infrared band.Therefore, the photoelectric conversion technique of sun power mainly contains the photovoltaic cell that utilizes uv-vis spectra and the thermo-electric conversion that utilizes infrared heat energy.Yet photovoltaic cell not only can't absorb the above infrared spectra of 800nm in solar spectrum, and the used heat that infrared spectra produces also will cause the bulk temperature of photovoltaic cell to rise, and then cause power conversion efficiency (pce) decline 5-15% left and right.
On the other hand, in theory, most solar radiation can be converted to heat energy.By thermoelectric effect, the thermograde that solar thermal energy produces can be converted to electric energy, has reported at present many Thermoelectric Generators, and due to the restriction of himself material behavior, its efficiency of conversion is less than 5%.Therefore, in order to realize the full spectrum utilization of solar spectrum, people are assembled into a system by photovoltaic cell and Thermoelectric Generator and carry out the conversion of solar spectrum, and solar spectrum is divided into UV spectrum and infrared spectra by a beam splitting lens by it.UV spectrum is partly changed for the absorption of photovoltaic cell, and infrared light is partly for the thermo-electric device thermo-electric conversion.Yet, nearly all solar photothermoelectric system is all the macroscopic view combination of discrete photovoltaic cell and thermo-electric device, and unrealized material horizontal is integrated, absorption and the utilization that therefore still can't really solve the full spectrum of sun power, the heat effect that the infrared spectra that can't absorb produces also will reduce power conversion efficiency (pce) simultaneously.
In order in a material, solar spectrum to be carried out to the conversion of full spectrum, realize that in solar spectrum, photo-thermal is changed simultaneously.We have designed the integrated material of photoelectric material and thermoelectric material, utilize best photovoltaic material CdTe and thermoelectric material Bi
2te
3, (CdTe is in bottom, Bi for the integrated design by current carrier
2te
3on top), utilize magnetron sputtering method, successfully prepared CdTe nanometer stick array and stratiform Bi
2te
3integrated material.Through showing CdTe/Bi
2te
3the electrical integrated material of photo-thermal can convert the light and heat in solar spectrum to electric energy simultaneously, realizes that collaborative the enhancing reaches the collaborative effect of utilizing conversion of photo-thermal.
Summary of the invention
We utilize the p-n junction principle, have designed photothermal integrated formed material, and its substrate is conductive glass, the CdTe that lower floor is p-type, the Bi that upper strata is N-shaped
2te
3.CdTe and Bi
2te
3form a p-n junction.Its concrete structure as shown in Figure 1.When sunlight, during from back side illuminaton, p-n junction produces photovoltaic effect, mainly absorbs Uv and visible light, and the sense of current of generation as shown in Figure 1.Simultaneously, the infrared band that is greater than 800nm in solar spectrum will produce heat, and in p-n junction, the heat of the compound generation of current carrier is also by the Bi be delivered to
2te
3bottom, so just at Bi
2te
3two ends up and down form a temperature difference, thermoelectric material Bi
2te
3to also convert this temperature difference to electric energy, the sense of current as shown in Figure 1 simultaneously.CdTe/Bi like this
2te
3integrated material is when carrying out opto-electronic conversion by solar spectrum, also also convert the heat energy produced in the heat energy in solar spectrum and p-n junction photoelectric conversion process to electric energy simultaneously, and the sense of current of conversion is consistent, realize collaborative the enhancing, obtain the collaborative effect of utilizing of solar energy optical-thermal.
Therefore, invention has designed a kind of collaborative cadmium telluride (CdTe) nanometer rod/Tellurobismuthite (Bi that utilizes effect of photo-thermal that has
2te
3) integrated material of laminate structure, and successfully realize design by magnetron sputtering, characterize the ability of having confirmed the collaborative conversion solar light and heat of integrated material by the V-t curve.
Technical scheme of the present invention is as follows:
A kind of have a collaborative integrated nanometer structured material of cadmium telluride/Tellurobismuthite of sending a telegraph of photo-thermal, it is deposition one deck cadmium telluride nanometer rod layer on the conducting surface of conducting glass substrate, deposit again the Tellurobismuthite layer of tellurium doping on cadmium telluride nanometer rod layer surface, form the integrated nanometer structured material of cadmium telluride/Tellurobismuthite.
The integrated nanometer structured material of above-mentioned cadmium telluride/Tellurobismuthite, described cadmium telluride nanometer rod bed thickness 2000-3000 nanometer.
The integrated nanometer structured material of above-mentioned cadmium telluride/Tellurobismuthite, described Tellurobismuthite bed thickness 300-1500 nanometer.
The integrated nanometer structured material of above-mentioned cadmium telluride/Tellurobismuthite, the volatilization of tellurium element that described Tellurobismuthite layer process tellurium has adulterated post-compensation, the atomicity ratio is bismuth: tellurium=2:2.9～2:3.15.
The integrated nanometer structured material of above-mentioned cadmium telluride/Tellurobismuthite, draw wire as positive pole at the Tellurobismuthite layer with elargol, draw wire with elargol and form battery as negative pole on the conducting surface of conducting glass substrate, as shown in Figure 1, when sunlight is injected and produced voltage and current from the conductive glass face.
A kind of method for preparing the integrated nanometer structured material of above-mentioned cadmium telluride/Tellurobismuthite, it is at magnetic as shown in Figure 2
In the control sputtering instrument, carry out, it comprises the steps:
The preparation of step 1. cadmium telluride nanometer rod
1.1 the cadmium telluride target is put on the radio frequency platform 1 of vacuum chamber 7 of magnetic control sputtering device;
1.2 conducting glass substrate is positioned on sample table 2;
1.3 regulate the distance of sample table 2 and radio frequency platform 1 to 80-90mm, preferably 88-90mm;
1.4 vacuum chamber is vacuumized, thereby makes the vacuum tightness in vacuum chamber reach 2.0 * 10
-4pa～4.0 * 10
-4pa;
1.5 conducting glass substrate is heated to 350-400 ℃, with the crystallization condition of regulation and control cadmium telluride;
1.6 be filled with argon gas in vacuum chamber, and ar pressure is adjusted to 0.4-1.0Pa, 0.4-0.5Pa preferably, the scattering degree of the cadmium telluride sputtered out with adjusting in the process that arrives electrically-conductive backing plate, thus regulate sedimentation rate;
1.7 apply radio-frequency voltage in the negative electrode 10 of target immediately and 11, the anode (being voltage of alternating current) after substrate immediately, the adjusting radio-frequency current is 81-140mA, preferably 130-140mA; Voltage is 0.37-0.60kV, 0.58-0.60kV preferably, make argon gas ionization, utilize the positive negativity generating period of AC power alternately, when sputtering target during in positive half cycle, stream of electrons is to target surface, neutralize the positive charge of its surface accumulation, and accumulation electronics, make its surface present negative bias, cause when the negative half-cycle of radio-frequency voltage attracting the argon ion bombardment target, thus realize radio-frequency sputtering pass through the size of radio-frequency current voltage (being alternating current and voltage of alternating current size) thus regulates and how many adjusting sedimentation rates of the CdTe that can regulate and control to sputter out; Deposition 1-2 hour;
The preparation of step 2. Tellurobismuthite laminate structure
2.1 the Tellurobismuthite target is put on the direct current platform 12 of vacuum chamber 7 of magnetic control sputtering device; The tellurium target is put on the radio frequency platform 1 of magnetic control sputtering device simultaneously and (the cadmium telluride target is replaced) and carried out dual-target sputtering;
2.1 step 1 having been deposited to the conducting glass substrate of cadmium telluride is positioned on sample table 2;
2.2 regulate the distance of sample table and radio frequency platform to 80-90mm, preferably 88-90mm;
2.3 vacuum chamber is vacuumized, thereby makes the vacuum tightness in vacuum chamber reach 2.0 * 10
-4pa～4.0 * 10
-4pa;
2.4 conducting glass substrate is heated to 350-450 ℃, with the crystallization condition of regulation and control Tellurobismuthite;
2.5 be filled with argon gas in vacuum chamber, and ar pressure is adjusted to 1.5-2.0Pa, 1.9-2.0Pa preferably, the scattering degree of the Tellurobismuthite sputtered out with adjusting in the process that arrives electrically-conductive backing plate, thus regulate sedimentation rate;
2.6 the adjusting radio-frequency current is 95-100mA, preferably 99-100mA; Voltage is 0.38-0.42kV, preferably 0.39-0.40kV;
2.7 the adjusting galvanic current is 80-100mA, preferably 80-90mm; Voltage is 0.25-0.27kV, preferably 0.25-0.26kV;
Deposition 1-2 hour, make the integrated nanometer structured material of described cadmium telluride/Tellurobismuthite.
Cadmium telluride (CdTe) nanometer rod/Tellurobismuthite (Bi obtained
2te
3) integrated material of laminate structure can convert the light and heat in solar spectrum to electric energy simultaneously, realizes the collaborative effect of utilizing conversion of photo-thermal.
The accompanying drawing explanation
Fig. 1 is the battery structure schematic diagram of material of the present invention and its composition.
Fig. 2 is the schematic diagram of magnetic control sputtering device (JGP-450a type multi-target magnetic control sputtering depositing system, Chinese Academy of Sciences Shenyang scientific instrument development center company limited), and wherein: 1 is the radio frequency platform; 2 is sample table; 3 is baffle plate; 4 is the argon inlet mouth; 5 is mass flowmeter; 6 is vacuum extractor (comprising mechanical pump and molecular pump); 7 is vacuum chamber; 8 is the sample table axis of rotation; 9 for adding the thermal control power supply; 10 is radio frequency platform negative electrode; 11 is anode; 12 is the direct current platform; 13 is direct current platform negative electrode.
Fig. 3 is the XRD figure of the product that adopts the method for embodiments of the invention to make.
Fig. 4 is the stereoscan photograph of embodiment 1.
Fig. 5 is the stereoscan photograph partial enlarged drawing of embodiment 1.
Fig. 6 is the V-t curve that obtains the collaborative utility of product photo-thermal electricity.Its test condition is that its intensity of illumination of xenon lamp is 8mW/cm
2.
Fig. 7 is the V-t curve that obtains the collaborative utility of product photo-thermal electricity.Its test condition is that its intensity of illumination of xenon lamp is 25mW/cm
2.
Fig. 8 is the V-t curve that obtains the collaborative utility of product photo-thermal electricity.Its test condition is that its intensity of illumination of xenon lamp is 50mW/cm
2.
Fig. 9 is the V-t curve that obtains the collaborative utility of product photo-thermal electricity.Its test condition is that its intensity of illumination of halogen lamp is 8mW/cm
2.
Figure 10 is the V-t curve that obtains the collaborative utility of product photo-thermal electricity.Its test condition is that its intensity of illumination of halogen lamp is 25mW/cm
2.
Figure 11 is the stereoscan photograph of embodiment 2.
Embodiment
The present invention adopts two step magnetron sputtering methods preparations to have the method for the collaborative special nanostructure cadmium telluride that utilizes effect of photo-thermal/Tellurobismuthite integrated material
In the present invention, the resistance of CdTe target is larger, and the magnetically controlled sputter method therefore adopted is radio-frequency sputtering.On the contrary, Bi
2te
3the resistance of target is less, and the magnetically controlled sputter method therefore adopted is d.c. sputtering, wherein during dual-target sputtering the Te target for to Bi
2te
3adulterated, adopted radio-frequency sputtering.
By reference to the accompanying drawings 2, the technical scheme that two step magnetron sputtering methods according to an embodiment of the invention prepare cadmium telluride (nano-wire array)/Tellurobismuthite (stratiform) is:
Cadmium telluride target (as commercial cadmium telluride target) is put on the radio frequency platform 1 of vacuum chamber 7 of magnetic control sputtering device, conducting glass substrate is positioned on sample table 2, regulate sample table 2 and radio frequency platform 1 apart from d to predetermined distance (d=80-90mm) in this scope, thereby the CdTe that makes to sputter out arrives the distance of substrate, drop in suitable scope;
Open 6 pairs of vacuum chambers 7 of vacuum extractor and vacuumize the anti-oxidation preparing for next step pours argon gas of deflating, make the interior vacuum tightness of vacuum chamber 7 reach preset value (as 2.0 * 10
-4pa～4.0 * 10
-4pa);
Open and add the thermal control power supply, and start the sample table axis of rotation 8 and make substrate carry out rotation with certain speed, so that the film of deposition is comparatively even, allow the electrically-conductive backing plate temperature rise to 350 ℃-400 ℃ crystallization conditions with regulation and control CdTe;
Regulating argon flow amount by mass flowmeter 5 is 25sccm.
Open argon inlet mouth 4, in vacuum chamber 7, be filled with argon gas, thereby and adjustable pressure be that 0.4-1.0Pa can regulate the CdTe that the sputters out scattering degree in arriving the substrate process and regulates sedimentation rate;
Butterfly 3 is by target and conducting glass substrate isolation
Apply radio-frequency voltage (being voltage of alternating current and electric current) in the negative electrode 10 of target immediately with immediately between the anode 11 after substrate, the adjusting radio-frequency current is 81mA-140mA, voltage is 0.37kV-0.60kV, utilize the positive negativity generating period of AC power alternately, when sputtering target during in positive half cycle, stream of electrons is to target surface, neutralize the positive charge of its surface accumulation, and accumulation electronics, make its surface present negative bias, cause attracting the argon ion bombardment target when the negative half-cycle of radio-frequency voltage, thereby realize radio-frequency sputtering; By the size to the radio frequency current/voltage (being alternating current and voltage of alternating current size), regulated, thus the CdTe that sputters out of regulation and control the number regulate sedimentation rate; (as figure) butterfly 3, to the contact vacuum-chamber wall, makes the CdTe sputtered out can arrive conducting glass substrate clockwise;
Deposition 1-2 hour;
Prepare completely, close radio-frequency power supply;
To be cooled to room temperature, take out the cadmium telluride target
Tellurobismuthite target (as commercial Tellurobismuthite target) is put on the direct current platform 12 of vacuum chamber 7 of magnetic control sputtering device, tellurium target (as commercial tellurium target) is put on the radio frequency platform 1 of vacuum chamber 7 of magnetic control sputtering device simultaneously, conducting glass substrate is positioned on sample table 2, keep the constant apart from d of sample table 2 and radio frequency platform 1, thereby make the Bi sputtered out
2te
3the distance that arrives substrate with Te drops in suitable scope;
Open 6 pairs of vacuum chambers 7 of vacuum extractor and vacuumize the anti-oxidation preparing for next step pours argon gas of deflating, make the interior vacuum tightness of vacuum chamber 7 reach preset value (as 2.0 * 10
-4pa～4.0 * 10
-4pa);
Open and add the thermal control power supply, and start sample and make substrate carry out rotation with certain speed from turntable 8, so that the film of deposition is comparatively even, allow the electrically-conductive backing plate temperature rise to 350 ℃-450 ℃ with regulation and control Bi
2te
3crystallization condition with Te;
Regulating argon flow amount by mass flowmeter 5 is 25sccm.
Open argon inlet mouth 4, in vacuum chamber 7, be filled with argon gas, and adjustable pressure is that 1.5-2.0Pa can regulate the Bi sputtered out
2te
3thereby regulate sedimentation rate with the scattering degree of Te in arriving the substrate process;
Apply radio-frequency voltage (being voltage of alternating current and electric current) in the negative electrode 10 of target immediately with immediately between the anode 11 after substrate, the adjusting radio-frequency current is 95mA-100mA, voltage is 0.38kV-0.42kV, apply volts DS and electric current in the negative electrode 13 of target immediately with immediately between the anode 11 after substrate simultaneously, the adjusting galvanic current is 80mA-100mA, voltage is 0.25kV-0.27kV, is regulated the Bi that regulation and control sputter out by the size to radio frequency current/voltage and galvanic current/voltage
2te
3thereby with Te the number regulate sedimentation rate; (as figure) butterfly 3, to the contact vacuum-chamber wall, makes the Bi sputtered out clockwise
2te
3can arrive CdTe nano-wire array surface with Te;
Deposition 1-2 hour;
Prepare completely, close radio frequency and direct supply;
In preparation method of the present invention, first to regulate the size apart from d, sputtering pressure, substrate temperature, radio-frequency power supply of sample table 2 and radio frequency platform (sputtering source) 1, then starting sputter can control to obtain and be deposited on the cadmium telluride nano-wire array on conducting glass substrate, the cadmium telluride nanometer stick array structure homogeneous that makes magnetron sputtering deposition make, effectively guaranteed being uniformly distributed of nanophase.In like manner, be applicable to the preparation of stratiform Tellurobismuthite structure.
The result of the experiment of carrying out according to the inventor, during preparation CdTe nanometer rod, sample table 2 is about 88-90mm with the preferred distance of radio frequency platform 1, preferably the sputter operating air pressure is about 0.4-0.5Pa, preferably the radio-frequency sputtering electric current is about 130-140mA, preferably sputtering voltage is about 0.58-0.60kV, and the preferred substrate temperature is in about 350-400 ℃ scope; Under these preferred parameters, resulting nanorod structure is homogeneous more, and effect is better.Preparation laminate structure Bi
2te
3during nanometer rod, sample table 2 is about 88-90mm with the preferred distance of radio frequency platform 1, preferably the sputter operating air pressure is about 1.9-2.0Pa, preferably the d.c. sputtering electric current is about 80-90mA, preferably d.c. sputtering voltage is about 0.25-0.26kV, preferably the radio-frequency sputtering electric current is about 99-100mA, and preferably radio-frequency sputtering voltage is about 0.39-0.40kV, and the preferred substrate temperature is in about 350-450 ℃ scope; Under these preferred parameters, resulting Bi
2te
3the laminate structure effect is better.
Embodiment 1:
(1) preparation of the integrated nanometer structured material of cadmium telluride/Tellurobismuthite
Regulate sample table 2 and radio frequency platform 1 apart from d=90mm
Open and add thermal control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 350 ℃;
Be filled with argon gas toward vacuum chamber 7, and adjustable pressure is 0.4Pa;
The adjusting radio-frequency current is 140mA, and voltage is 0.60kV
Depositing time 2h;
Prepare completely, close radio-frequency power supply, naturally cool to 25 ℃ of room temperatures, take out target;
By Bi
2te
3target is positioned on the direct current platform, the Te target is positioned on the radio frequency platform simultaneously, and vacuum chamber 7 is vacuumized, and makes the interior vacuum tightness of vacuum chamber 7 reach 3.4 * 10
-4pa;
Open and add thermal control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 350 ℃;
Be filled with argon gas toward vacuum chamber 7, and adjustable pressure is 2.0Pa;
The adjusting galvanic current is 80mA, and voltage is 0.25kV;
The adjusting radio-frequency current is 100mA, and voltage is 0.40kV;
Depositing time 1h;
Prepare completely, close radio-frequency power supply, naturally cool to 25 ℃ of room temperatures;
(2) sample characterization
Adopt X-ray diffractometer to carry out material phase analysis, as shown in Figure 3, illustrate that material (00l) the direction directional property made is strong the cadmium telluride that makes/Tellurobismuthite integrated material.The integrated material that above-mentioned magnetron sputtering method is made is observed under scanning electronic microscope, success obtains the appearance structure of cadmium telluride nanorod structure and Tellurobismuthite laminate structure integrated material, stereoscan photograph as shown in Figures 4 and 5, show cadmium telluride nanometer rod bed thickness 2000 nanometers, Tellurobismuthite bed thickness 300 nanometers.
With energy spectrometer, the Tellurobismuthite laminate structure is analyzed, result shows bismuth: tellurium=2:2.96.
Integrated material is carried out to V-t curve sign, and testing method as shown in Figure 1.At first adopting the xenon lamp that thermal value is few is 8mW/cm at power
2irradiated, as shown in Figure 6, when rayed, transient voltage increases rapidly the graph of a relation of time and voltage, and it is p-n junction photovoltaic effect, after along with the increase of light application time, voltage is comparatively steady, when low light intensity is described, heat is less, thermoelectric effect is not obvious.When strengthening xenon lamp power to 25mW/cm
2the time, as shown in Figure 7, the transient voltage value is than 8mW/cm
2shi Shangsheng, light application time increases voltage and steadily descends, and is obvious photovoltaic property, illustrates that heat is less, and thermoelectric effect is still less to be not enough to balance photovoltaic effect and to descend with the rising of heat.When the xenon lamp increased power to 50mW/cm
2the time, as shown in Figure 8, moment illumination magnitude of voltage further promotes, and along with the growth of time, voltage continues to raise, and thermoelectric effect starts to manifest the effect that realizes the collaborative utilization of photo-thermal.
For further confirmatory experiment result, we have adopted the halogen lamp that heat is large to be irradiated, when intensity of illumination is 8mW/cm
2the time, as shown in Figure 9, when rayed, transient voltage increases to rapidly a definite value to the graph of a relation of time and voltage, under same intensity of illumination, and the minimizing of different ultraviolet-visible spectrum wave bands, its photovoltaic effect weakens, so its transient voltage value is little than xenon lamp.Along with the increase of light application time, voltage is also along with slowly increasing to certain value, and its result shows, thermoelectric effect is obvious, has realized the collaborative effect of utilizing of photo-thermal.When intensity of illumination increases to 25mW/cm
2the time, as shown in figure 10, the transient voltage value is than 8mW/cm
2in time, significantly increase, and thermoelectric effect continuation increasing, more manifested the collaborative effect of utilizing of photo-thermal.
Embodiment 2:
(1) preparation of the integrated nanometer structured material of cadmium telluride/Tellurobismuthite
Regulate sample table 2 and radio frequency platform 1 apart from d=90mm
Open and add thermal control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 400 ℃;
Pour argon gas toward vacuum chamber 7, and adjustable pressure is 0.4Pa;
The adjusting radio-frequency current is 130mA, and voltage is 0.60kV
Depositing time 1.5h;
Prepare completely, close radio-frequency power supply, naturally cool to 25 ℃ of room temperatures, take out target;
By Bi
2te
3target is positioned on the direct current platform, the Te target is positioned on the radio frequency platform simultaneously, and vacuum chamber 7 is vacuumized, and makes the interior vacuum tightness of vacuum chamber 7 reach 3.4 * 10
-4pa;
Open and add thermal control power supply 9, and open sample from turntable 8, allow base reservoir temperature rise to 450 ℃;
Pour argon gas toward vacuum chamber 7, and adjustable pressure is 2.0Pa;
The adjusting galvanic current is 80mA, and voltage is 0.25kV;
The adjusting radio-frequency current is 100mA, and voltage is 0.40kV;
Depositing time 1.5h;
Prepare completely, close radio-frequency power supply, naturally cool to 25 ℃ of room temperatures;
Change CdTe and Bi
2te
3thereby depositing time change thickness proportion, the scanning electron microscope (SEM) photograph of the product of acquisition as shown in figure 11, shows cadmium telluride nanometer rod bed thickness 2200 nanometers, Tellurobismuthite bed thickness 1300 nanometers.
With energy spectrometer, the Tellurobismuthite laminate structure is analyzed, result shows bismuth: tellurium=2:3.1.
At sputter Bi
2te
3process in be equivalent to that CdTe is had to an annealing process, and Bi
2te
3sputtering time increases, so CdTe nanometer stick array structure has agglomeration.And Bi
2te
3there is the CdTe layer below, so base reservoir temperature and Bi
2te
3growth temperature a thermograde is arranged, therefore under comparatively high temps, Bi
2te
3can keep stratiform, and some variation of CdTe nanometer stick array structure.But its product still has the light-heat integration performance, meet the integrated material principle design.
From above-described embodiment, we can find out the structure that having of embodiment 1 is best, and XRD illustrates that its directional property is also fine, and embodiment 1 adopts optimized parameter scope deposit film, therefore obtain best effect.Simultaneously, the microstructure change of tube material or thickness proportion change, as long as consistent with the principle of integrated material design, just can obtain the collaborative ability of changing of light and heat.
Claims (5)
1. one kind has the collaborative integrated nanometer structured material of cadmium telluride/Tellurobismuthite of sending a telegraph of photo-thermal, it is characterized in that: it is deposition one deck cadmium telluride nanometer rod layer on the conducting surface of conducting glass substrate, deposit again the Tellurobismuthite layer of tellurium doping on cadmium telluride nanometer rod layer surface, form the integrated nanometer structured material of cadmium telluride/Tellurobismuthite.
2. the integrated nanometer structured material of cadmium telluride/Tellurobismuthite according to claim 1, is characterized in that: described cadmium telluride nanometer rod bed thickness 2000-3000 nanometer.
3. the integrated nanometer structured material of cadmium telluride/Tellurobismuthite according to claim 1, is characterized in that: described Tellurobismuthite bed thickness 300-1500 nanometer.
4. the integrated nanometer structured material of cadmium telluride/Tellurobismuthite according to claim 1 is characterized in that: described Tellurobismuthite layer through tellurium doping post-compensation the volatilization of tellurium element, the atomicity ratio is bismuth: tellurium=2:2.9～2:3.15.
5. a method for preparing the integrated nanometer structured material of cadmium telluride/Tellurobismuthite claimed in claim 1, it carries out in magnetic control sputtering device, it is characterized in that it comprises the steps:
The preparation of step 1. cadmium telluride nanometer rod
1.1 the cadmium telluride target is put on the radio frequency platform 1 of vacuum chamber 7 of magnetic control sputtering device;
1.2 conducting glass substrate is positioned on sample table 2;
1.3 regulate the distance of sample table 2 and radio frequency platform 1 to 80-90mm, preferably 88-90mm;
1.4 vacuum chamber is vacuumized, thereby makes the vacuum tightness in vacuum chamber reach 2.0 * 10
-4pa～4.0 * 10
-4pa;
1.5 conducting glass substrate is heated to 350-400 ℃, with the crystallization condition of regulation and control cadmium telluride;
1.6 be filled with argon gas in vacuum chamber, and ar pressure is adjusted to 0.4-1.0Pa, 0.4-0.5Pa preferably, the scattering degree of the cadmium telluride sputtered out with adjusting in the process that arrives electrically-conductive backing plate, thus regulate sedimentation rate;
1.7 apply radio-frequency voltage in the negative electrode 10 of target immediately and 11, the anode (being voltage of alternating current) after substrate immediately, the adjusting radio-frequency current is 81-140mA, preferably 130-140mA; Voltage is 0.37-0.60kV, 0.58-0.60kV preferably, make argon gas ionization, utilize the positive negativity generating period of AC power alternately, when sputtering target during in positive half cycle, stream of electrons is to target surface, neutralize the positive charge of its surface accumulation, and accumulation electronics, make its surface present negative bias, cause when the negative half-cycle of radio-frequency voltage attracting the argon ion bombardment target, thus realize radio-frequency sputtering pass through the size of radio-frequency current voltage (being alternating current and voltage of alternating current size) thus regulates and how many adjusting sedimentation rates of the CdTe that can regulate and control to sputter out; Deposition 1-2 hour;
The preparation of step 2. Tellurobismuthite laminate structure
2.1 the Tellurobismuthite target is put on the direct current platform 12 of vacuum chamber 7 of magnetic control sputtering device; The tellurium target is put on the radio frequency platform 1 of magnetic control sputtering device simultaneously and (the cadmium telluride target is replaced) and carried out dual-target sputtering;
2.1 step 1 having been deposited to the conducting glass substrate of cadmium telluride is positioned on sample table 2;
2.2 regulate the distance of sample table and radio frequency platform to 80-90mm, preferably 88-90mm;
2.3 vacuum chamber is vacuumized, thereby makes the vacuum tightness in vacuum chamber reach 2.0 * 10
-4pa～4.0 * 10
-4pa;
2.4 conducting glass substrate is heated to 350-450 ℃, with the crystallization condition of regulation and control Tellurobismuthite;
2.5 be filled with argon gas in vacuum chamber, and ar pressure is adjusted to 1.5-2.0Pa, 1.9-2.0Pa preferably, the scattering degree of the Tellurobismuthite sputtered out with adjusting in the process that arrives electrically-conductive backing plate, thus regulate sedimentation rate;
2.6 the adjusting radio-frequency current is 95-100mA, preferably 99-100mA; Voltage is 0.38-0.42kV, preferably 0.39-0.40kV;
2.7 the adjusting galvanic current is 80-100mA, preferably 80-90mm; Voltage is 0.25-0.27kV, preferably 0.25-0.26kV;
Deposition 1-2 hour, make the integrated nanometer structured material of described cadmium telluride/Tellurobismuthite.
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Cited By (5)
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| CN104152851A (en) * | 2014-08-15 | 2014-11-19 | 浙江工贸职业技术学院 | Method for manufacturing tellurium elementary substance nano materials of controllable structure |
| CN106498354A (en) * | 2016-09-18 | 2017-03-15 | 中国科学院电工研究所 | A kind of method for preparing hexagonal Spiral morphology Tellurobismuthite. thermal electric film |
| CN108486530A (en) * | 2018-03-16 | 2018-09-04 | 成都理工大学 | The method that on-line heating realizes the transformation of glass Be2Ti3 film p-n junctions |
| CN109950138A (en) * | 2019-04-11 | 2019-06-28 | 广东工业大学 | A kind of nanometer column array heterojunction and preparation method thereof |
| CN113398904A (en) * | 2021-05-06 | 2021-09-17 | 桂林电子科技大学 | Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds) |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152851A (en) * | 2014-08-15 | 2014-11-19 | 浙江工贸职业技术学院 | Method for manufacturing tellurium elementary substance nano materials of controllable structure |
| CN104152851B (en) * | 2014-08-15 | 2016-08-24 | 浙江工贸职业技术学院 | A kind of preparation method of structure-controllable tellurium simple substance nanometer material |
| CN106498354A (en) * | 2016-09-18 | 2017-03-15 | 中国科学院电工研究所 | A kind of method for preparing hexagonal Spiral morphology Tellurobismuthite. thermal electric film |
| CN106498354B (en) * | 2016-09-18 | 2018-09-25 | 中国科学院电工研究所 | A method of preparing hexagonal Spiral morphology bismuth telluride thermal electric film |
| CN108486530A (en) * | 2018-03-16 | 2018-09-04 | 成都理工大学 | The method that on-line heating realizes the transformation of glass Be2Ti3 film p-n junctions |
| CN109950138A (en) * | 2019-04-11 | 2019-06-28 | 广东工业大学 | A kind of nanometer column array heterojunction and preparation method thereof |
| CN113398904A (en) * | 2021-05-06 | 2021-09-17 | 桂林电子科技大学 | Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds) |
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