CN109103272A - A kind of N-CDs/PVP film, fluorescent solar collector with high-photoelectric transformation efficiency and preparation method thereof - Google Patents
A kind of N-CDs/PVP film, fluorescent solar collector with high-photoelectric transformation efficiency and preparation method thereof Download PDFInfo
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- 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
- H01L31/02—Details
- H01L31/0232—Optical elements or arrangements associated with the device
- H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
Abstract
The invention belongs to new material technology fields, and in particular to a kind of N-CDs/PVP film, fluorescent solar collector with high-photoelectric transformation efficiency and preparation method thereof.The present invention is using nitrogen-doped carbon quantum dot as fluorescent particle, and PVP is as film adjuvants, and the N-CDs/PVP film UV-Vis absorption region provided is wider, film transmission rate is higher, PL transmitting light is stronger etc..Thus the fluorescent solar concentrator photovoltaic high conversion efficiency provided.
Description
Technical field:
The invention belongs to new material technology fields, and in particular to a kind of N-CDs/PVP film, can fluorescence radiation there is height
Fluorescent solar collector of photoelectric conversion efficiency and preparation method thereof.
Background technique:
For the sustainable development for guaranteeing energy and environment, greatly developing clean energy resource and renewable energy becomes the world today
The basis of energy policy.In numerous renewable and clean energy resources, environmentally friendly and safe solar energy is due to rich reserves, by people
Be considered as can long-term sustainable utilization the ideal energy.It mainly include at present photoelectric conversion and two kinds of photothermal conversion to the utilization of solar energy
Mode, wherein photoelectric conversion is realized by way of solar energy power generating.Photovoltaic power generation is that current solar energy is best
One of Land use systems, but cost of electricity-generating is high, the price is very expensive for the solar battery of unit area, even if solar battery
Photoelectric conversion efficiency is being gradually increased, but its cost performance is still very low.Based on this reason, there has been proposed the think ofs of optically focused
Road, i.e., the sunlight irradiated large area, gathers together and is irradiated to above a fritter solar battery, to improve on unit area
Intensity of illumination on solar battery improves the cost performance of solar energy power generating to improve the utilization rate of solar battery.
In the 1970s, Weber and Goetzberger propose a kind of novel concentrating solar photovoltaic device
Part --- solar energy fluorescence collector (Luminescent Solar Concentrators, LSCs), mainly by fluorescent material,
Transparent medium and solar battery three parts are constituted.The principle of solar energy fluorescence collector is that fluorescent material is mixed transparent medium
(such as glass, PMMA) or the surface that fluorescent material is coated in transparent medium is fabricated to fluorescent flat optical waveguide, utilizes phosphor
Material absorbs the radiation of specific band in solar spectrum, then launches the fluorescence of red shift of wavelength with higher fluorescence quantum efficiency, leads to
The transparent medium for crossing optical waveguide is transmitted to side, concentrates the solar battery for being coupled into the appropriate bandgap of optical waveguide side stickup
In, it is converted into power output.Since the refractive index of optical waveguide is greater than the refractive index of air, belong to optically denser medium, therefore fluorescence meeting
Roundtrip or directive side transmission of being all-trans, only seldom fluorescence can escape into air from optical waveguide in optical waveguide
In, to ensure that effective collecting action to sunlight.
The photoelectric conversion efficiency of LSCs dependent on optical waveguide to the capacity gauge of sunlight and the optical characteristics of fluorescent material,
And the most of optical waveguide material such as refractive index of glass, PMMA and PVP is all 1.5 or so, therefore their receipts to sunlight
Collection ability is not much different, so people have concentrated on focus on the suitable fluorescent material of searching.Organic fluorescence materials due to
Fluorescence quantum efficiency is high, is easy the advantages that obtaining and is cheapness, is applied in LSCs by people earliest.However as grinding in recent years
For the persons of studying carefully to the numerous studies of organic fluorescence materials, they have found that the spectral absorption range of most of organic fluorescence materials is small, and
Absorption peak is in visible light wave range, results in the near infrared band that photon is most intensive in solar spectrum and is not efficiently used, limit
The raising of LSCs efficiency is made；In addition the fluorescence emission peak of most of organic fluorescence materials is in visible light wave range, this with it is most strong
The crystal silicon solar energy battery pole that spectral response is located near infrared band mismatches, and the photoelectricity for greatly limiting solar battery turns
Efficiency is changed, to influence the efficiency of LSCs.
Summary of the invention:
The purpose of the present invention is to solve the shortcomings of the prior art and providing a kind of nitrogen-doped carbon quantum dot/PVP film, tool
There is the fluorescent solar collector and preparation method thereof of high-photoelectric transformation efficiency.
A kind of N-CDs/PVP film, nitrogen-doped carbon quantum dot in the N-CDs (nitrogen-doped carbon quantum dot)/PVP film
Content be 0.1-0.7%.
According to the above scheme, the N-CDs/PVP film is molten by nitrogen-doped carbon quantum dot is dispersed in PVP/ ethyl alcohol
Then liquid is obtained in substrate surface spin coating using spin-coating method, interlayer heat treatment, the N doping carbon amounts of acquisition is carried out in spin coating process
Sub- point/PVP film is with a thickness of 8-93 μm.
The preparation method of N-CDs/PVP film, the steps include:
Using citric acid as carbon source, urea prepares good dispersion, partial size point as N doping raw material, using a step microwave method
The N-CDs carbon quantum dot of cloth 2-8nm；
Then N-CDs/PVP film is formed on substrate: substrate surface and surrounding are pre-processed, while by N doping
Carbon quantum dot is dispersed in PVP/ ethanol solution, then using spin-coating method in substrate surface spin coating nitrogen-doped carbon quantum dot
PVP/ ethanol solution carries out interlayer heat treatment in spin coating process, can be obtained lower turn of different-thickness by spin coating difference number
Change the N-CDs/PVP film of light.
According to the above scheme, the N-CDs carbon quantum dot the preparation method comprises the following steps: prepare citric acid concentration be 50-60wt% and
Urea concentration is the solution of 20-30wt%, then 750-850W microwave reaction 5-6min, the small molecule of vacuum drying removal remaining
Substance obtains N-CDs carbon quantum dot.
According to the above scheme, the substrate is ultra-clear glasses.
According to the above scheme, substrate pretreatment includes that surrounding polishes and is cleaned by ultrasonic, wherein ultrasonic cleaning includes deionized water
20min is cleaned, acetone cleans 20min, and ethyl alcohol cleans 20min.
According to the above scheme, the concentration of the PVP/ ethanol solution be 0.2-0.8g/ml, preferably 0.3-0.4g/ml, it is described
The carbon quantum dot mass fraction being dispersed therein is 0.1-1.0%, preferably 0.3-0.7%.
According to the above scheme, the spin coating revolving speed of the PVP/ ethanol solution of each spin coating nitrogen-doped carbon quantum dot and time are spin coating
Revolving speed is 1000-4000rpm, time 20s-50s, preferably are as follows: 1000-3000rpm elder generation spin coating 5-10s, then 2000-
4000rpm spin coating 10-40s；More preferably 2000rpm*5s+3500rpm*30s.
According to the above scheme, it after each spin coating, being heat-treated through interlayer, the interlayer heat treatment temperature is 30-70 DEG C, when
Between be 10-30min, carry out spin coating next time again after interlayer heat treatment, different-thickness can be obtained by spin coating difference number
The luminous N-CDs/PVP film fluorescence solar collector of lower conversion.
According to the above scheme, the spin coating number is 1-10 times, preferably 3-9 times.
Fluorescent solar collector, including N-CDs/PVP film and the solar battery assembled with it, by by N-CDs/
PVP film and solar battery assembling gained.
The present invention using nitrogen-doped carbon quantum dot as fluorescent particle, PVP as film adjuvants, regulate and control the concentration of PVP with
And the concentration of nitrogen-doped carbon quantum dot, controllably obtain the N- that gained film is uniform, transparent, surfacing energy fluorescence radiation
CDs/PVP film, film thickness are turned between tens microns, and then based on this solar collector photoelectricity obtained at several microns
Change high-efficient.Specifically, in forming N-CDs/PVP film, too low carbon in the PVP/ ethanol solution of nitrogen-doped carbon quantum dot
Quantum dot content fluorescence intensity is low, and excessively high carbon quantum dot concentration can bring it about reunion, leads to fluorescent quenching.Except this, revolve
Painting condition also influences the surface smoothness of film, additionally by the thickness of regulation spincoating conditions and the also controllable film of spin coating number
Degree；Meanwhile the dosage of PVP will affect the viscosity of spin coating liquid, also can thickness to spin-coated thin film and flatness have a significant impact, such as
Embodiment 10 causes polymer film too thin since PVP concentration is too low, so that film fluorescence solar collector performance is not
It is good.Heat treatment and film thickness etc. also have a great impact to the apparent property of product and final performance.It is suitable by regulating and controlling
Heat treatment condition to film hardening, on the one hand can guarantee the surface smoothness of film, on the other hand can eliminate inside film
Defect improves reflection of the light inside film, to influence final photoelectric conversion efficiency.The applicant is eventually by regulation spin coating
The selection of condition, heat treatment condition, the film number of plies, carbon quantum dot concentration, the Alternatives Parameter Conditions such as PVP concentration is prepared
The film of the surfacing with suitable thickness of high fluorescent effect, to be finally obtained the film fluorescence sun haveing excellent performance
It can collector.
Compared with prior art, the invention has the benefit that
1. the present invention, using nitrogen-doped carbon quantum dot as fluorescent particle, PVP is as film adjuvants, the N-CDs/ that provides
PVP film UV-Vis absorption region is wider, film transmission rate is higher, PL transmitting light is stronger etc..Thus the fluorescent solar provided
Concentrator photovoltaic high conversion efficiency, the LSCs various aspects of performance prepared by nitrogen-doped carbon quantum dot is also opposite to be improved.In addition, this hair
It is bright to select nitrogen-doped carbon quantum dot as fluorescent particle, compared to conventional semiconductors quantum dot, the low, chemical stability with toxicity
The advantages that high, easily prepared.
2. selecting PVP as film forming agent, efficiently solves N doping carbon dots and divide in the existing polymer film-forming agent such as PMMA
The problem that property is poor, fluorescence intensity is low is dissipated, and PVP is non-toxic and tasteless, carries out testing the actual bodily harm that can reduce to experimenter using it.
3. the inorganic-quantum-dot in present invention preparation is using citric acid as carbon source, urea is as N doping raw material, using letter
Single convenient and fast step microwave method is prepared for N-CDs, has obtained inexpensively, good dispersion, particle diameter distribution is narrow, performance difference between official written reply
Small, absorption peak is probably located at the N-CDs of 350nm, stable product quality.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture and grain size distribution for the N-CDs that embodiment 1 is prepared.
Fig. 2 is that the N-CDs/PVP film fluorescence solar collector that embodiment 2 is prepared is respectively in excitation wavelength
PL spectrum under 290-500nm.
Fig. 3 be the N-CDs/PVP film fluorescence solar collector that is prepared of embodiment 2,3,4,5 and blank sample (no
Carbon containing quantum dot) absorption spectrum comparison.
Fig. 4 is the N-CDs/PVP film fluorescence solar collector and blank sample that embodiment 4,6,7,8,9 is prepared
The absorption spectrum comparison of (being free of carbon quantum dot).
Fig. 5 be the N-CDs/PVP film fluorescence solar collector that is prepared of embodiment 2,3,4,5 and blank sample (no
Carbon containing quantum dot) J-V curve.
Fig. 6 is the J-V curve for the N-CDs/PVP film fluorescence solar collector that embodiment 4,6,7,8,9 is prepared.
Specific embodiment
Embodiment 1
It takes 10mL pure water to be added in 50mL beaker, sequentially adds 3.0g citric acid and 2.0g urea, ultrasonic 5min is obtained
Then clear solution is placed in the micro-wave oven of 800W and carries out heating 5min by clear transparent solutions, it can be observed that solution colour
Starting change palm fibre finally has a briquetting body to be formed, and then puts it into 1h in 50 DEG C of vacuum oven, to remove small point of remaining
Sub- substance.With the aqueous solution of needle cylinder type filter membrane filter (0.22 μm) Purification by filtration carbon quantum dot, the N-CDs finally obtained is solid
Body powder, is easily dispersed in dehydrated alcohol, pays attention to being protected from light storage.The transmission electron microscope picture and grain size distribution of N-CDs is shown in Fig. 1.
Embodiment 2
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot (the nitrogen-doped carbon quantum dot of embodiment 1) that mass fraction is 0.1% is added, and
Ultrasonic 20min keeps its evenly dispersed.Plated film is carried out using spin-coating method, revolving speed and time are 2000rpm*5s+3500rpm*30s,
The heat treatment of 50 DEG C of * 15min is finally carried out on hot plate.
Embodiment 3
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.3% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, revolving speed and time are 2000rpm*5s+3500rpm*30s, finally carry out 50 DEG C of * on hot plate
The heat treatment of 15min.
Embodiment 4
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, revolving speed and time are 2000rpm*5s+3500rpm*30s, finally carry out 50 DEG C of * on hot plate
The heat treatment of 15min.
Embodiment 5
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.7% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, revolving speed and time are 2000rpm*5s+3500rpm*30s, finally carry out 50 DEG C of * on hot plate
The heat treatment of 15min.
Embodiment 6
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, and revolving speed and time are 2000rpm*5s+3500rpm*30s, every to have plated one layer and carry out on hot plate
The heat treatment of 50 DEG C of * 15min repeats 3 plated films and heat treatment operation.
Embodiment 7
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, and revolving speed and time are 2000rpm*5s+3500rpm*30s, every to have plated one layer and carry out on hot plate
The heat treatment of 50 DEG C of * 15min repeats 5 plated films and heat treatment operation.
Embodiment 8
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, and revolving speed and time are 2000rpm*5s+3500rpm*30s, every to have plated one layer and carry out on hot plate
The heat treatment of 50 DEG C of * 15min repeats 7 plated films and heat treatment operation.
Embodiment 9
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.4g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, and revolving speed and time are 2000rpm*5s+3500rpm*30s, every to have plated one layer and carry out on hot plate
The heat treatment of 50 DEG C of * 15min repeats 9 plated films and heat treatment operation.
Embodiment 10
Substrate is pre-processed first, including surrounding polishing and ultrasonic cleaning (deionized water 20min, acetone 20min,
Ethyl alcohol 20min).Then the PVP of corrresponding quality is added in the ethyl alcohol of certain volume, for heating stirring to being completely dissolved, solution is dense
Degree is 0.3g/ml；The nitrogen-doped carbon quantum dot that mass fraction is 0.5% is added, and ultrasound 20min keeps its evenly dispersed.Benefit
Plated film is carried out with spin-coating method, and revolving speed and time are 2000rpm*5s+3500rpm*30s, every to have plated one layer and carry out on hot plate
The heat treatment of 50 DEG C of * 15min repeats 7 plated films and heat treatment operation.
Embodiment 11
Film side obtained by above-described embodiment (embodiment 2-10) is connected into monocrystalline silicon battery, N-CDs/PVP can be carried out
The photoelectric efficiency of film fluorescence solar collector is tested.The N-CDs/PVP film fluorescence that the embodiment of the present invention 2 is prepared is too
The PL spectrum such as Fig. 2 of positive energy collector in the case where excitation wavelength is respectively 290-500nm, it is seen that sample is to wavelength 290-
The exciting light of 500nm has fluorescence response；The UV-visible absorption spectrum for the sample that each embodiment is prepared such as Fig. 3,4,
It can be seen that sample has more apparent absorption peak at 370nm, and increase with carbon quantum dot point concentration, the film number of plies, absorption peak
Enhance；The N-CDs/PVP film fluorescence solar collector and blank sample (being free of carbon dots) that embodiment 2,3,4,5 is prepared
J-V curve such as Fig. 4, it is seen that with carbon quantum dot concentration increase, sample photoelectric efficiency first increases to be reduced afterwards, and carbon quantum dot concentration is
Photoelectric efficiency reaches best when 0.5%.The N-CDs/PVP film fluorescence solar energy collecting that embodiment 4,6,7,8,9 is prepared
J-V curve such as Fig. 6 of device, it is seen that increase with the film number of plies, sample photoelectric efficiency first increases to be reduced afterwards, 7 layers of sample photoelectric efficiency
Reach best.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (10)
1. a kind of N-CDs/PVP film, it is characterised in that: the content of nitrogen-doped carbon quantum dot in the N-CDs/PVP film
For 0.1-1.0%.
2. N-CDs/PVP film according to claim 1, it is characterised in that: carbon quantum in the N-CDs/PVP film
Point mass score is 0.3-0.7%；Then it utilizes spin coating by nitrogen-doped carbon quantum dot is dispersed in PVP/ ethanol solution
Method is obtained in substrate surface spin coating, and interlayer heat treatment, nitrogen-doped carbon quantum dot/PVP film of acquisition are carried out in spin coating process
With a thickness of 8-93 μm.
3. the preparation method of N-CDs/PVP film as claimed in claim 2, it is characterised in that: step are as follows:
Using citric acid as carbon source, urea prepares good dispersion, particle diameter distribution 2- as N doping raw material, using a step microwave method
The N-CDs carbon quantum dot of 8nm；
Then N-CDs/PVP film is formed on substrate: substrate surface and surrounding are pre-processed, while by N doping carbon amounts
Son point is dispersed in PVP/ ethanol solution, then utilizes spin-coating method in the PVP/ second of substrate surface spin coating nitrogen-doped carbon quantum dot
Alcoholic solution carries out interlayer heat treatment in spin coating process, the fluorescence radiation of different-thickness can be obtained by spin coating difference number
N-CDs/PVP film.
4. according to the method described in claim 3, it is characterized by: wherein: the N-CDs carbon quantum dot the preparation method comprises the following steps:
The solution that citric acid concentration is 50-60wt% and urea concentration is 20-30wt% is prepared, then 750-850W microwave reaction 5-
6min, the small-molecule substance of vacuum drying removal remaining, obtains N-CDs carbon quantum dot；
The substrate is ultra-clear glasses；Substrate pretreatment include surrounding polish and be cleaned by ultrasonic, wherein ultrasonic cleaning include go from
Sub- water cleans 20min, and acetone cleans 20min, and ethyl alcohol cleans 20min.
5. according to the method described in claim 3, it is characterized by: the concentration of the PVP/ ethanol solution be 0.2-0.8g/ml,
The carbon quantum dot mass fraction being dispersed therein is 0.1-1.0%.
6. according to the method described in claim 3, it is characterized by: the PVP/ ethanol solution of each spin coating nitrogen-doped carbon quantum dot
Spin coating revolving speed and the time be 1000-3000rpm elder generation spin coating 5-10s, then 2000-4000rpm spin coating 10-40s.
7. according to the method described in claim 3, it is characterized by: being heat-treated every time through interlayer, the interlayer after spin coating
Heat treatment temperature is 30-70 DEG C, time 10-30min, carries out spin coating next time after interlayer heat treatment again, not by spin coating
The N-CDs/PVP film fluorescence solar collector to shine with the lower conversion that different-thickness can be obtained in number.
8. according to the method described in claim 3, it is characterized by: the spin coating number is 1-10 times.
9. according to the method described in claim 3, it is characterized by: the concentration of the PVP/ ethanol solution be 0.3-0.4g/ml,
The carbon quantum dot mass fraction being dispersed therein is 0.3-0.7%, and the spin coating number is 3-9 times.
10. fluorescent solar collector, it is characterised in that: including N-CDs/PVP film and the solar battery assembled with it, by
N-CDs/PVP film and solar battery assembling gained.
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