CN104310304A - Preparation method of nano column array with controllable size and surface structure - Google Patents

Preparation method of nano column array with controllable size and surface structure Download PDF

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Publication number
CN104310304A
CN104310304A CN201410564829.4A CN201410564829A CN104310304A CN 104310304 A CN104310304 A CN 104310304A CN 201410564829 A CN201410564829 A CN 201410564829A CN 104310304 A CN104310304 A CN 104310304A
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China
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sio
column array
nano
particle
etching
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CN201410564829.4A
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Inventor
张朝
郭坤平
陈长博
李炜玲
张静
徐韬
魏斌
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a preparation method of a nano column array with controllable size and surface structure. The preparation method comprises the following steps: carrying out surface modification on SiO2 nano particles so that the SiO2 nano particles have amphipathicity, namely hydrophily and hydrophobicity; depositing a SiO2 single-layer film on a substrate by adopting a Langmuir-Blodget film technology; etching SiO2 by adopting an isotropic reaction ion etching technology to further change the sizes of the SiO2 nano particles; carrying out silicon etching on the deposited SiO2 nano particles which are used an etching mask plate by adopting an isotropic deep reaction ion etching technology and an induction coupling plasma etching technology; and etching the residual SiO2 nano particles by hydrofluoric acid and finally obtaining the nano column array with the controllable size and surface structure. According to the preparation method of the nano column array with the controllable size and surface structure, the limitation caused by the limitation of electron beam lithography and a batch machining method is effectively overcome; the surface reflectivity of solar cells can be effectively reduced; and the photovoltaic conversion efficiency of the solar cells is improved.

Description

The nano column array preparation method of controlled dimensions and surface texture
Technical field
The present invention relates to a kind of preparation technology of semi-conductor electronic device, particularly relate to a kind of preparation and Optimization Technology of Semiconductor substrate, be applied to solar cell preparing technical field.
Background technology
Solar energy as a kind of can the clean energy resource of continuous utilization, have huge application potential.Current photovoltaic market, still based on first generation solar-electricity prepared by crystalline silicon, but by Shockley-Queisser effect restriction the not high crystalline silicon of photoelectric transformation efficiency in theory the limit be 33.7%.In order to further develop photovoltaic industry, the photoelectric transformation efficiency of solar cell must be improved and reduce costs.In the eurypalynous nano material of crowd, Si nano column array obtains in recent years by means of the column construction of its one dimension, unique electricity and optical property and pays close attention to widely and deep research, particularly has very large potential using value in solar cell application aspect.
Silicon nano-pillar/line obtains in recent years by means of the column construction of its one dimension, unique electricity and optical property and pays close attention to widely and deep research, such as in solar cell, field-effect transistor, biology sensor, luminescent material etc., achieve certain achievement, particularly in solar cell application aspect, there is very large potential using value.At present, for high efficiency silicon solar cells, its surface reflectivity is one of key factor affecting cell photoelectric conversion efficiency, and the textured structure of nano-pillar/linear array can reduce the surface reflectivity of solar cell effectively.
At present, prepare the method that silicon nano-pillar/linear array can adopt and mainly contain two kinds: chemical attack and physical etchings.Silicon nano-pillar/line is prepared with chemical corrosion method by the seminar of most domestic, although chemical corrosion method is simple to operation, but its physical chemical mechanism waits further exploratory development, and the silicon nano-pillar/line of preparation has of low quality, blemish is more, and physical dimension is the shortcoming such as controlled not easily.Compare, the standby nano-pillar/line structure size of physical etchings legal system, surface topography are easy to control, and technique used also matches with traditional semiconductor technology.But the cost of physical etchings is higher, the nano-pillar obtained/line limited height and etch plasma bombardment used and can cause the lattice defect of substrate thus the electric property that can affect nano-pillar/line.Therefore, how to realize nano-pillar/linear array low cost controlled synthesis and improve its surface texture be still current nano-pillar/line apply in solar cell in technical barrier urgently to be resolved hurrily.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, the nano column array preparation method of a kind of controlled dimensions and surface texture is provided, effectively overcome the restriction of electron beam exposure high cost and batch processing method, controlled dimensions and controlled surface structure silicon nano column array can be prepared on substrate, effectively can reduce the surface reflectivity of solar cell, improve the photoelectric transformation efficiency of solar cell.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A nano column array preparation method for controlled dimensions and surface texture, comprises the following steps:
I. to the SiO of nano-particle solution 2particle carries out surface modification, makes it have amphiphilic, then adopts Langmuir-Blodgett membrane process, makes to have amphiphatic SiO 2particle obtains SiO at deposited on substrates 2monofilm; Adopt Langmuir-Blodgett membrane process at deposited on substrates SiO 2in particle process, for the SiO of 900nm level 2particle, the surface pressure preferably adopted controls at 10 ~ 14mN/m, and for the SiO of 600nm level 2particle, the surface pressure preferably adopted controls at 2.5 ~ 4mN/m; The material of substrate preferably adopts silicon, germanium, III-V race's semi-conducting material, organic semiconducting materials or semiconductor composite;
II. adopt isotropic reactive ion etching process, to the SiO on the substrate prepared in described step I 2monofilm etches, adjustment SiO 2the size of particle and particle gap, to SiO 2monofilm carries out pattern modification, makes SiO 2monofilm forms the etching mask plate of substrate; Adopt the SiO in isotropic reactive ion etching process etched substrate 2during monofilm, etching gas preferably adopts CHF 3and O 2mist, and the air pressure of etch chamber is 250mTorr, RF power is 100W;
III. by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts anisotropic deep reaction ion etch process to carry out etch substrate, prepares the nano column array of hackly surface, now SiO 2particle stays the top of nano-pillar; When adopting anisotropic deep reaction ion etch process to carry out etch substrate, etching gas preferably adopts SF 6and O 2mist, and passivation gas C 4f 8, etching power is 2100W, and passivation power is 2200W;
IV. by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts sense coupling technique to carry out etch substrate, prepares the nano column array of flat surface, now SiO 2particle stays the top of nano-pillar; Adopt sense coupling technique to carry out etch substrate, etching gas preferably adopts Cl 2for 30sccm, and in etch chamber, pressure is 10 mTorr, and etching power is 40W;
V. be positioned in hydrofluoric acid solution by the substrate with nano column array obtained in described step III or step IV, removing remains in the SiO at nano column array top 2particle, finally obtains the substrate of the Si nano column array with required size and surface texture.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the preparation technology of nano column array of the present invention, to combine with the lithographic technique of " from top to bottom " with the Nanosphere lithography technique of " from bottom to top " and prepares nano column array, obtain the nano column array of controlled dimensions and controlled surface structure;
2. the present invention selects Langmuir-Blodgett membrane technology to prepare mask plate, avoids electron beam lithography, reduces preparation cost;
3. the present invention can obtain different surface textures as required by selecting the different lithographic technique of DRIE and ICP two kinds;
4. the present invention is by selecting initial different size SiO 2nano particle and isotropic reactive ion etching time control diameter and the gap of nano-pillar, to make the preparation of mask plate convenient and reliable;
5. the present invention is by controlling the height of anisotropic DRIE or ICP etch period control Si nano-pillar, can need acquisition controlled dimensions and controlled surface structure nano post array, to meet the needs of different solar cells according to different.
Accompanying drawing explanation
Fig. 1 is the process chart of the nano column array preparation method of preferred embodiment of the present invention controlled dimensions and surface texture.
Fig. 2 is the SEM figure of silicon nano column array prepared by the preferred embodiment of the present invention.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
In the present embodiment, see Fig. 1 and Fig. 2, the nano column array preparation method of a kind of controlled dimensions and surface texture, comprises the following steps:
I. select the SiO being respectively 400nm and 900nm containing particle diameter 2the solution of nano particle, to the SiO of nano-particle solution 2particle carries out surface modification, makes it have hydrophilic and hydrophobic amphiphilic, then adopts Langmuir-Blodgett membrane process, will containing SiO 2the solution of nano particle drops on the surface of distilled water in Langmuir-Blodgett groove 1; Along T 2and T 2direction, compression Langmuir-Blodgett groove 1, makes the surface area of Langmuir-Blodgett groove 1 reduce, and surface pressing increase, in certain surface pressure limit, Si substrate 2 deposits SiO 2nano particle 3, the direction of scheming the v in b in Fig. 1 upwards at the uniform velocity lifts Si substrate 2, makes to have amphiphatic SiO 2particle obtains SiO at deposited on substrates 2monofilm, see the figure a in Fig. 1, figure b and figure c.
II. obtain, on Si substrate 2, adopting isotropic reactive ion etching process after step I, to the SiO on the Si substrate 2 prepared in described step I 2monofilm etches, adjustment SiO 2the size of nano particle 3 and particle gap, to SiO 2monofilm carries out pattern modification, makes SiO 2monofilm forms the etching mask plate of substrate, see figure d.Etching gas is CHF 3and O 2mist, it etches SiO 2it is main chemical etching.The air pressure of etch chamber is 250mTorr, RF power is 100W.
III. in order to obtain the silicon nano-pillar 4 compared with high length-diameter ratio, by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts anisotropic deep reaction ion etch process DRIE to carry out etch substrate, prepares the silicon nano column array of hackly surface, now SiO 2nano particle 3 stays the top of silicon nano-pillar 4.DRIE is a technology most characteristic in MEMS processing technology, generally adopts the process technology that the passivation of Bosch etching replaces.After being cleaned up by the Si substrate 2 obtained after step II, deep reaction ion etching technology is used to etch Si, as shown in the figure e in Fig. 1.In experimentation, the STS DRIE system etching system that uses, etching gas is SF 6and O 2mist, passivation gas is C 4f 8, etching power is 2100W, and passivation power is 2200W.First, etch step utilizes SF 6si substrate 2 is once etched; Then technique is switched to passivation step, C 4f 8si substrate 2 forms layer protective layer; After etching and passivation hocket, form high length-diameter ratio, finally obtain high etch rate, good anisotropic perfect adaptation.Controlled the length of silicon nano-pillar 4 by etch period, etch the Si nano column array of Micro-scale length.
IV. in order to improve the surface texture quality of silicon nano-pillar, by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts sense coupling technique ICP to carry out etch substrate, prepares the silicon nano column array of flat surface, now SiO 2nano particle 3 stays the top of silicon nano-pillar 4.ICP etching can provide higher plasma density and independently substrate bias source control owing to having simultaneously, can obtain suitable etch rate, thus can obtain lower etching injury, be more conducive to control surface structure under lower bias voltage.After being cleaned up by the Si substrate 2 obtained after step 2, inductively coupled plasma (inductively coupled plasma, ICP) lithographic technique is used to etch Si, also as shown in the figure e in Fig. 1.In experiment, etching gas Cl2 is 30sccm, and in etch chamber, pressure is 10mTorr; Etching power is 40W.It longitudinally etches Si for main physical etch, and Selection radio is very large, and silicon nano-pillar 4 surface therefore etching out is more smooth.
V. the substrate with silicon nano column array obtained in described step III or step IV being positioned over mass percent concentration is keep 30s in 50% hydrofluoric acid solution, is remained in the SiO at silicon nano column array top by chemical attack removing 2nano particle 3, finally obtains the substrate of the Si nano column array with required size and surface texture, see figure f and Fig. 2 in Fig. 1.
The present embodiment, by controlling the height of anisotropic DRIE or ICP etch period control Si nano-pillar, can need acquisition controlled dimensions and controlled surface structure nano post array, to meet the needs of different solar cells, see Fig. 2 according to different.The present embodiment adopts the nanosphere of " from bottom to top " etching to combine with the etching technics of " from top to bottom ", the silicon nano-pillar array structure that preparation distributes in order.Replace electron beam lithography by selecting the Langmuir-Blodgett membrane technology in the Nanosphere lithography technique of " from bottom to top " and prepare mask plate, reduce cost; By the nano-pillar selecting different " from top to bottom " anisotropic lithographic techniques to obtain different surfaces structure, control the size that etch period controls nano column array.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all Spirit Essences according to technical solution of the present invention and principle, substitute, combination, to simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of the nano column array preparation method of controlled dimensions of the present invention and surface texture, all protection scope of the present invention is belonged to.

Claims (6)

1. a nano column array preparation method for controlled dimensions and surface texture, is characterized in that, comprise the following steps:
I. to the SiO of nano-particle solution 2particle carries out surface modification, makes it have amphiphilic, then adopts Langmuir-Blodgett membrane process, makes to have amphiphatic SiO 2particle obtains SiO at deposited on substrates 2monofilm;
II. adopt isotropic reactive ion etching process, to the SiO on the substrate prepared in described step I 2monofilm etches, adjustment SiO 2the size of particle and particle gap, to SiO 2monofilm carries out pattern modification, makes SiO 2monofilm forms the etching mask plate of substrate;
III. by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts anisotropic deep reaction ion etch process to carry out etch substrate, prepares the nano column array of hackly surface, now SiO 2particle stays the top of nano-pillar;
IV. by the SiO modified through pattern prepared in described step II 2monofilm, as etching mask plate, adopts sense coupling technique to carry out etch substrate, prepares the nano column array of flat surface, now SiO 2particle stays the top of nano-pillar;
V. be positioned in hydrofluoric acid solution by the substrate with nano column array obtained in described step III or step IV, removing remains in the SiO at nano column array top 2particle, finally obtains the substrate of the Si nano column array with required size and surface texture.
2. the nano column array preparation method of controlled dimensions and surface texture according to claim 1, is characterized in that: in described step I, adopt Langmuir-Blodgett membrane process at deposited on substrates SiO 2in particle process, for the SiO of 900nm level 2particle, the surface pressure of employing controls at 10 ~ 14mN/m, and for the SiO of 600nm level 2particle, the surface pressure of employing controls at 2.5 ~ 4mN/m.
3. the nano column array preparation method of controlled dimensions and surface texture according to claim 1, is characterized in that: in described step II, adopts the SiO in isotropic reactive ion etching process etched substrate 2during monofilm, etching gas is CHF 3and O 2mist, the air pressure of etch chamber is 250mTorr, RF power is 100W.
4. the nano column array preparation method of controlled dimensions and surface texture according to claim 1, it is characterized in that: in described step III, when adopting anisotropic deep reaction ion etch process to carry out etch substrate, etching gas is SF 6and O 2mist, passivation gas C 4f 8, etching power is 2100W, and passivation power is 2200W.
5. the nano column array preparation method of controlled dimensions and surface texture according to claim 1, is characterized in that: in described step IV, adopts sense coupling technique to carry out etch substrate, etching gas Cl 2for 30sccm, in etch chamber, pressure is 10 mTorr, and etching power is 40W.
6. according to the nano column array preparation method of controlled dimensions described in any one and surface texture in Claims 1 to 5, it is characterized in that: in described step I, the material of the substrate of employing is silicon, germanium, III-V race's semi-conducting material, organic semiconducting materials or semiconductor composite.
CN201410564829.4A 2014-10-22 2014-10-22 Preparation method of nano column array with controllable size and surface structure Pending CN104310304A (en)

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CN104709872A (en) * 2015-02-06 2015-06-17 中国科学院物理研究所 Diamond nanowire array and preparation method thereof, and electrode for electrochemical analysis
CN106115617A (en) * 2016-06-28 2016-11-16 北京随能科技有限公司 A kind of polymer nanocomposite post array without method for preparing template
CN106601836A (en) * 2016-12-16 2017-04-26 上海电机学院 Technology for manufacturing light trapping structure in surface of photovoltaic cell based on nano-particles
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709872A (en) * 2015-02-06 2015-06-17 中国科学院物理研究所 Diamond nanowire array and preparation method thereof, and electrode for electrochemical analysis
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CN106601836A (en) * 2016-12-16 2017-04-26 上海电机学院 Technology for manufacturing light trapping structure in surface of photovoltaic cell based on nano-particles
CN112326758A (en) * 2020-09-21 2021-02-05 江苏元上分子工程研究中心有限公司 Silicon nano biosensor, preparation method thereof and virus detection method
CN114813808A (en) * 2022-04-24 2022-07-29 胜科纳米(苏州)股份有限公司 Method for detecting cross-sectional structure of semiconductor chip

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Application publication date: 20150128