CN102183864A - Second-order nonlinear optical film material and preparation method thereof - Google Patents
Second-order nonlinear optical film material and preparation method thereof Download PDFInfo
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- CN102183864A CN102183864A CN2011100805647A CN201110080564A CN102183864A CN 102183864 A CN102183864 A CN 102183864A CN 2011100805647 A CN2011100805647 A CN 2011100805647A CN 201110080564 A CN201110080564 A CN 201110080564A CN 102183864 A CN102183864 A CN 102183864A
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Abstract
The invention provides a second-order nonlinear optical film material based on a p-n junction and a preparation method thereof. The second-order nonlinear optical film material is composed of more than one layer of film materials, an overlapped multilayer film material in a p/n.../p or n/p.../n form is respectively formed by a n-type or p-type semiconductor material; and the semiconductor material at least comprises a layer of p-type and a layer of n-type semiconductor film to form a p-n junction. The preparation method of the second-order nonlinear optical film material comprises a film system structure design and a preparation step of the second-order nonlinear optical film material. The nonlinear optical material of the structure is suitable for designing the second-order nonlinear optical material for high second-order harmonic generation, the practicality of frequency doubling efficiency can be adjusted by changing the thickness of the film and the layers of the film; and the product can be widely applied to the nonlinear optical field, such as laser frequency doubling and full-spectrum sunlight utilization.
Description
Technical field
The present invention relates to optical thin film material, particularly a kind of Second-order non-linear optical thin film material and preparation method thereof.
Background technology
Along with all-optical network is arrived in the develop rapidly of optical communication technique, photoswitch and array thereof become one of its core technology, also are one of principal elements that influences the optical-fiber network performance.And the condition precedent that light shutter device is moved is to prepare the nonlinear optical material of function admirable, therefore, nonlinear optical material has caused the great interest of people as the critical material in the photoelectron technology, developing high performance optical material with big nonlinear factor is one of current advanced subject, becomes the focus of various countries' scholar's research.Therefore, new optical-fiber network core devices technology has also proposed higher practicability to photoswitch and has required: on the technical indicator of photoswitch, require light shutter device to have higher operating rate, lower insertion loss and longer mission life; On the volume of device, because increasing of all optical network unit component for making device miniaturization, just requires device that higher integrated level is arranged; Aspect cost, because the expansion of network, required device will increase greatly, has also brought the high cost of optical network device thus.Therefore, must take technical measures, the development new technology reduces the cost of optical device, could be accepted by the user like this, is difficult to satisfy above-mentioned requirements with the photoswitch of traditional means manufacturing.
These technology are achieved, and the condition precedent that device is moved is to prepare the nonlinear optical material of function admirable, and nonlinear optical techniques such as optical sccond-harmonic generation, optical phase conjugation also will be more widely used in these devices.Nonlinear optical material has caused the great interest of people as the critical material in the photoelectron technology, the development of nonlinear optical material is one of current advanced subject, the various countries scholar has launched keen competition in this respect, haveing breakthrough aspect the photoelectric devices such as nonlinear optical material and photoswitch to hope, nearest Canadian Carleton University utilizes polymkeric substance and bucky-ball to make a kind of new compound substance, the University of Toronto has realized on the film made from this material that immediately beam of laser controls the motion of another Shu Jiguang, and this is a major progress of nonlinear optical material research field.China's research in this respect also is in international most advanced level, seminar as old wound day academician leader has invented nonlinear optical crystal BBO, the LBO etc. that are described as " China card crystal " in succession, and proposition " the anionic group theory of crystal nonlinear optical effect ", obtain very high praise at international academic community, be successfully used to instruct among the exploratory development of novel non-linearity optical material by external scientist.
Summary of the invention
Technical matters to be solved by this invention is: a kind of Second-order non-linear optical thin film material based on p-n junction and preparation method thereof is provided, this method is passed through the depletion layer built in field intensity of control Second-order non-linear optical thin film material, thereby obtains big SH(Second Harmonic) intensity.
The technical scheme that the present invention solves its technical matters employing is:
The present invention is to provide a kind of Second-order non-linear optical thin film material based on p-n junction, it is made of membraneous material more than 1 layer, forms p/n by n type and p N-type semiconductor N material respectively ... / p or n/p ... the overlapping multilayered film material of/n form.Wherein, described semiconductor material comprises the semiconductive thin film of one deck p type and one deck n type at least and constitutes p-n junction.
The thickness of every layer of semiconductive thin film can be 5nm～200nm.
Described semiconductor material can be crystalline state or amorphous all can be made into the semiconductor material of film.
Above-mentioned Second-order non-linear optical thin film material provided by the invention is applied to laser freuqency doubling or full spectrum sunshine utilization etc.
The preparation method of Second-order non-linear optical thin film material provided by the invention, its step comprises:
(1) film structure design:
By technological requirement design film structure, comprise the number of plies that changes thicknesses of layers and film; This film structure is for forming p/n by n type and p N-type semiconductor N material respectively ... / p or n/p ... the overlapping multilayered film material structure of/n form, and constitute p-n junction by the semiconductive thin film that comprises one deck p type and one deck n type at least;
(2) preparation of described Second-order non-linear optical thin film material:
Use crystalline state or amorphous all can be made into the semiconductor material of film, according to the film structure design of step (1), adopt the preparation of physics or chemical method, its prerequisite is to prepare the p-n junction semiconductive thin film that comprises one deck p type and one deck n type at least.
In the said method, the thickness of every layer of semiconductive thin film can be 5nm～200nm.
Described physical preparation method is meant vacuum sputtering, plasma film coating, vacuum evaporation of present use etc.
Described chemical preparation process is meant various chemical vapor deposition (CVD)s, sol-gel process of present use etc.
The Second-order non-linear optical thin film material of method for preparing provided by the invention is applied to laser freuqency doubling or full spectrum sunshine utilization etc.
The present invention compared with prior art has following main advantage:
Observe second order nonlinear optical effect according to the direct depletion layer p-n junction that produces of the semiconductor of different conduction-types, have considerable theory significance and practice significance: the correctness of verifying depletion layer p-n junction theoretical model on the one hand; On the other hand as a kind of new SHG(Second Harmonic Generation) technology, in conjunction with depletion layer p-n junction architectural feature, break through traditional acquisition amorphous state second-order non-linear optical materials and must carry out the thinking that nonlinear polarization is handled to material earlier, handle without nonlinear polarization, overcome the dependence of built in field to the nonlinear polarization condition, thereby can obtain big SH intensity by the depletion layer p-n junction built in field intensity of controlling effective doping control semiconductor material, prepare the Second-order non-linear optical thin film of high second order nonlinear coefficient, design and preparation for the amorphous state second-order non-linear optical materials simultaneously provides theoretic guidance foundation, satisfies the actual request for utilization to the amorphous state nonlinear optical material of optical waveguide and light shutter device.
In a word, the nonlinear optical material of structure of the present invention is suitable for the full wave double-frequency material of design preparation, can obtain the second-order non-linear optical materials that high second harmonic produces, Practical Performances such as shg efficiency can be regulated by the number of plies that changes thicknesses of layers and film, product will be widely used in non-linear optical field, as laser freuqency doubling and full spectrum sunshine utilization etc.
Description of drawings
Fig. 1 is that the second harmonic of 1#, 2#, 3# sample produces the Maker bar graph.
Fig. 2 is that the second harmonic of quartz crystal produces the Maker bar graph.
Embodiment
The present invention is based on following method and prepare a kind of high-level efficiency Second-order non-linear optical thin film material based on p-n junction: the built in field that produces in the glass after polarize according to a conventional method (1) is the cause of second order nonlinear optical effect, so according to the depletion layer model, use the different conduction-types semiconductor to form the built in field that P-N knot institute directly produces and also should be able to observe the second harmonic generation, so at first design suitable film structure for forming p/n by n type and p N-type semiconductor N material respectively ... / p or n/p ... the overlapping multilayered film material structure of/n form, and constitute p-n junction by the semiconductive thin film that comprises one deck p type and one deck n type; (2) use crystalline state or amorphous all can be made into the semiconductor material of film, and various physics or chemical plating method; (3) thickness of every layer film is 5nm～200nm.The present invention can obtain the nonlinear optical material that high second harmonic produces.
Below in conjunction with specific embodiment method provided by the invention is described further, but does not limit the present invention.
Embodiment 1:
Adopt PECVD method deposition P-N knot a-Si:H film, detailed process is: with clean-out system quartz glass plate is cleaned up, put into the beaker that ethanol is housed after distilled water is cleaned and clean 5min at ultrasonic cleaner, the oven dry back is as the substrate of amorphous silicon membrane.Deposition gas is that purity is 100% silane, and the hydrogen purity of using as diluted silane is 99.999%, and impurity gas feeds the reaction chamber gas flow and controlled by gas meter for the diluted in hydrogen degree is 3% borine and phosphine.With glass sheet by after going into sheet chamber access arrangement reaction chamber, vacuumize, in computerized equipment, behind the technological parameters such as the flow of setting silane and hydrogen and impurity gas, glow power, aura air pressure, underlayer temperature, deposition time, realize the automatic control of technological process by computer program.Deposition parameter is H
2/ SiH
4Throughput ratio 600/60 sccm, aura air pressure 100Pa, glow power 40W, 200 ℃ of underlayer temperatures.
In order to study P-N knot second order nonlinear optical effect, deposited P type amorphous si film 40nm, the P-N knot amorphous si film of N type amorphous si film 40nm, design component sees Table 1(sample 1#).Wherein: P type amorphous si film is to form by doping borine in silane, and doping content compares SiH
4: H
2: B
2H
6Be 1:10:0.0075.N type amorphous si film is to form by doping phosphine in silane, and doping content compares SiH
4: H
2: PH
3Be 1:10:0.0075.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen, in the 1# sample, observed high second harmonic and produced, draw χ by the film computing formula
(2)Be 115.9 pm/V.
Embodiment 2:
Concrete coating process parameter has deposited P type amorphous si film 40nm with embodiment 1, the P-N knot amorphous si film of N type amorphous si film 40nm, design component sees Table 1(sample 2#).Wherein P type amorphous si film is to form by doping borine in silane, and doping content compares SiH
4: H
2: B
2H
6Be 1:10:0.008.N type amorphous si film is to form by doping phosphine in silane, and doping content compares SiH
4: H
2: PH
3Be 1:10:0.008.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen, in the 2# sample, observed high second harmonic and produced, its signal intensity ratio 1# sample is strong, draws χ by the film computing formula
(2)Be 347.7 pm/V.
Embodiment 3:
Concrete coating process parameter has deposited P type amorphous si film 40nm with embodiment 1, the P-N knot amorphous si film of N type amorphous si film 40nm, design component sees Table 1(sample 3#).Wherein P type amorphous si film is to form by doping borine in silane, and doping content compares SiH
4: H
2: B
2H
6Be 1:10:0.01.N type amorphous si film is to form by doping phosphine in silane, and doping content compares SiH
4: H
2: PH
3Be 1:10:0.01.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen, in the 3# sample, observed high second harmonic and produced, its signal intensity ratio 2# sample is strong, draws χ by the film computing formula
(2)Be 521.5 pm/V.
Embodiment 4:
Concrete coating process parameter has deposited P type amorphous si film 40nm with embodiment 1, and no N type amorphous si film amorphous si film does not promptly have P-N to generate in the film, and design component sees Table 1(sample 4#).Wherein P type amorphous si film is to form by doping borine in silane, and doping content compares SiH
4: H
2: B
2H
6Be 1:10:0.0075.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen owing to do not have P-N to generate in the film, in the 4# sample, do not observe second harmonic produce.
Embodiment 5:
Concrete coating process parameter has deposited N type amorphous si film 40nm with embodiment 1, and no P type amorphous si film does not promptly have P-N to generate in the film, and design component sees Table 1(sample 5#).Wherein N type amorphous si film is to form by doping phosphine in silane, and doping content compares SiH
4: H
2: PH
3Be 1:10:0075.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen, in the 5# sample, do not observe second harmonic and produce.
Embodiment 6:
In order to prove the existence of built in field in the P-N knot amorphous si film, because amorphous si film is a highly resistant material, directly there is difficulty in concrete coating process parameter by electrical method proof built in field with embodiment 1.Therefore, prepared 6# P-I-N type amorphous si film, P type amorphous si film 15nm wherein, N type amorphous si film 20nm, I is an intrinsic layer, I layer 200nm, design component sees Table 1(sample 6#).Wherein: P type amorphous si film is to form by doping borine in silane, and doping content compares SiH
4: H
2: B
2H
6Be 1:10:0.0075.N type amorphous si film is to form by doping phosphine in silane, and doping content compares SiH
4: H
2: PH
3Be 1:10:0.0075.The I layer does not mix.Can prove the existence of built in field in the P-N knot amorphous si film by the open-circuit voltage of P-I-N type amorphous si film under the test illumination condition.
The test result of sample nonlinear effect is seen Fig. 1, by among Fig. 1 as can be seen, in the 6# sample, do not observe second harmonic and produce.
Embodiment 7:
Second-order non-linear optical thin film material can be applied to laser freuqency doubling, and promptly when laser passed through this film, laser frequency produced frequency multiplication, and corresponding wavelength becomes former wavelength half, has realized laser freuqency doubling, widens laser wavelength range.
Embodiment 8:
Second-order non-linear optical thin film material, can be applied to the utilization of full spectrum sunshine, promptly when solar cell adds this function film, when solar irradiation is mapped to solar cell, for the long wavelength light (as infrared band) of sunshine spectrum, because the second nonlinear frequency-doubled effect of this film, long wavelength light (as infrared band) becomes short-wavelength light (as visible light wave range), improve the sunshine utilization ratio, thereby improved the solar cell utilization ratio.
Subordinate list
The doping content of table 1 design sample and deposit thickness
| Sample | P layer thickness (nm) | I layer thickness (nm) | N layer thickness (nm) | Doping content compares SiH 4:H 2:B 2H 6(or PH 3) |
| 1# | 40 | 0 | 40 | 1:10:0.0075 |
| 2# | 40 | 0 | 40 | 1:10:0.008 |
| 3# | 40 | 0 | 40 | 1:10:0.01 |
| 4# | 40 | 0 | 0 | 1:10:0.0075 |
| 5# | 0 | 0 | 40 | 1:10:0.0075 |
| 6# | 15 | 200 | 20 | 1:10:0.0075 |
Claims (7)
1. Second-order non-linear optical thin film material, it is characterized in that a kind of Second-order non-linear optical thin film material based on p-n junction, it is made of membraneous material more than 1 layer, form p/n by n type and p N-type semiconductor N material respectively ... / p or n/p ... the overlapping multilayered film material of/n form, wherein, described semiconductor material comprises the semiconductive thin film of one deck p type and one deck n type at least and constitutes p-n junction.
2. Second-order non-linear optical thin film material according to claim 1, the thickness that it is characterized in that every layer of semiconductive thin film is 5nm～200nm.
3. Second-order non-linear optical thin film material according to claim 1, it is characterized in that semiconductor material be crystalline state or amorphous all can be made into the semiconductor material of film.
4. the purposes of a Second-order non-linear optical thin film material is characterized in that the described Second-order non-linear optical thin film material of arbitrary claim in the claim 1 to 3, and it is applied to laser freuqency doubling or full spectrum sunshine utilization.
5. the preparation method of a Second-order non-linear optical thin film material is characterized in that this method step comprises:
(1) film structure design:
By technological requirement design film structure, comprise the number of plies that changes thicknesses of layers and film; This film structure is for forming p/n by n type and p N-type semiconductor N material respectively ... / p or n/p ... the overlapping multilayered film material structure of/n form, and constitute p-n junction by the semiconductive thin film that comprises one deck p type and one deck n type at least;
(2) preparation of described Second-order non-linear optical thin film material:
Use crystalline state or amorphous all can be made into the semiconductor material of film, according to the film structure design of step (1), adopt the preparation of physics or chemical method, its prerequisite is to prepare the p-n junction semiconductive thin film that comprises one deck p type and one deck n type at least.
6. according to the preparation method of the described Second-order non-linear optical thin film material of claim 1, it is characterized in that: the thickness of every layer of semiconductive thin film is 5nm～200nm.
7. the purposes of a Second-order non-linear optical thin film material is characterized in that the Second-order non-linear optical thin film material with claim 5 or 6 preparations, and it is applied to laser freuqency doubling or full spectrum sunshine utilization.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104659141A (en) * | 2015-03-07 | 2015-05-27 | 顾海涛 | High-efficiency solar battery covering frequency doubling crystals |
| CN105483826A (en) * | 2016-01-19 | 2016-04-13 | 武汉科技大学 | Application of KHgI3*H2O crystals in second-order non-linear optical field |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167353A (en) * | 1996-04-30 | 1997-12-10 | 朗迅科技公司 | Saturated Bragg reflector structure and making technology |
-
2011
- 2011-03-31 CN CN2011100805647A patent/CN102183864A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167353A (en) * | 1996-04-30 | 1997-12-10 | 朗迅科技公司 | Saturated Bragg reflector structure and making technology |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库信息科技辑》 20071115 王明亮 《铅硼玻璃及P-N结无定型硅薄膜的SHG研究》 40-44 1-2，4，6-7 , 第5期 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104659141A (en) * | 2015-03-07 | 2015-05-27 | 顾海涛 | High-efficiency solar battery covering frequency doubling crystals |
| CN105483826A (en) * | 2016-01-19 | 2016-04-13 | 武汉科技大学 | Application of KHgI3*H2O crystals in second-order non-linear optical field |
| CN105483826B (en) * | 2016-01-19 | 2018-12-18 | 武汉科技大学 | Application of the one water potassium triiodomercurate crystal in second nonlinear optic field |
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Application publication date: 20110914 |