CN116190490A - Method for preparing nanowire array device from bottom to top through Ti-assisted directional growth - Google Patents

Method for preparing nanowire array device from bottom to top through Ti-assisted directional growth Download PDF

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CN116190490A
CN116190490A CN202310127810.2A CN202310127810A CN116190490A CN 116190490 A CN116190490 A CN 116190490A CN 202310127810 A CN202310127810 A CN 202310127810A CN 116190490 A CN116190490 A CN 116190490A
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nanowire
substrate
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王志海
周洁
高志远
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Beijing University of Technology
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Abstract

A method for preparing a nanowire array device by Ti-assisted directional growth from bottom to top relates to the field of ultraviolet detection and the technical field of nano materials. Etching the photoresist-free part of the substrate to obtain a plurality of pit arrays, sequentially sputtering a metal layer Ti 1-5 nm and Au 5-15 nm from bottom to top in the pits to obtain a patterned Ti/Au catalyst array, and removing the photoresist; placing the substrate sputtered with Ti and Au in the pit into a high-temperature tube furnace; growing ZnO nanowires in a high-temperature tube furnace by a CVD method; according to the invention, under the action of the Ti/Au catalytic layer, the ZnO nanowire with good crystallization quality is simply and easily obtained in one step by a CVD method, and the ZnO nanowire is directly contacted with Si to obtain a heterojunction, so that secondary treatment is avoided, and finally the nanowire array device is obtained.

Description

Method for preparing nanowire array device from bottom to top through Ti-assisted directional growth
Technical Field
The invention relates to the field of ultraviolet detection and the technical field of nano materials, in particular to a method for realizing self-organizing preparation of a nanowire array function and an intelligent device from bottom to top by utilizing metal Ti to assist in directional growth of a ZnO nanowire array in a Chemical Vapor Deposition (CVD) method.
Background
The current preparation method of the nano device mainly comprises the steps of 'top-down' and 'bottom-up'
Two, wherein the top-down method generally prepares the zinc oxide raw material into a one-dimensional nano structure through photoetching, ion implantation and other processes, and the stable zinc oxide nano wire is prepared by depending on the advancement of the process, so that the reliability and the repeatability are very dependent on equipment with higher cost; the method from bottom to top forms the high-quality nanowire by utilizing the split combination of molecules and atoms, has good stability and has wide application in preparing the zinc oxide nanowire.
The bottom-up method is further classified into a gas phase method, a liquid phase method and a solid phase method according to the transportation mode of the reaction precursor. Wherein the vapor phase method is a method for synthesizing a final product by transporting a precursor in a gas mode, the vapor phase method comprises a Chemical Vapor Deposition (CVD) method using a plurality of methods, and the growth mechanism of the nanowire in the current method for growing the zinc oxide nanowire based on the CVD method is VLS (gas)
-liquid-solid) growth mechanism: in the heating process, the Au catalyst covered on the substrate is firstly melted and polymerized into metal liquid drops, then the reaction material evaporated into gas phase from the source material is continuously absorbed, the gas phase component is firstly dissolved in the liquid phase catalyst particles and forms eutectic alloy liquid drops containing the catalyst and the target material, when the alloy liquid drops absorb the gas phase component to be supersaturated, the required nano material can generate crystal nucleus at the liquid-solid phase interface, one-dimensional nano linear material is separated and grown, the nano material is deposited on the interface of the liquid drops and the substrate, the nano material is continuously grown, and the metal particles are supported until the growth is stopped. Because the metal particles are always arranged at the top end of the nanowire in the growth process of the nanowire, the growth direction of the nanowire grown by the CVD method is difficult to control because the metal particles can be influenced by the force exerted by certain metal particles in the growth process. The zinc oxide nanowire is generally directionally grown by a multi-purpose hydrothermal method, but the growth time is long, the length-diameter ratio of the obtained nanowire is small, and the length-diameter ratio of the nanowire grown by the CVD method is larger, so that the nanowire is more favorable for light absorption, and the growth time is short and the quality is high. There have been studies in the past to control directional growth of ZnO nanowires by CVD, such as direct growth of ZnO nanowires on sapphire, but the resulting nanowires are still inclined to different degrees and have smaller aspect ratios, and sapphire only serves as a substrate on which the nanowires are grown and does not participate in conduction, while Si is selected as a substrate and also serves as one of the materials of the heterojunction.
In addition, in many researches, the ultraviolet detector for obtaining the heterojunction is subjected to secondary treatment, for example, after the ZnO nanowire is obtained, the nanowire is contacted with different substances through wet transfer or vapor deposition and other processes to obtain the heterojunction, and then the heterojunction is prepared into a complete device, so that the operation is complicated and the effect of the device is possibly influenced by pollution on the zinc oxide nanowire in the middle.
The traditional ultraviolet detection device works through an external power supply and is developed to a self-powered ultraviolet detection device later, and the improvement saves the consumption of energy. The self-powered detector converts optical signals into electric signals to be output under the condition of no externally applied bias voltage, the working principle is that when light irradiates a semiconductor, carriers are diffused to form a built-in electric field, and the built-in electric field has photo-generated electromotive force to form photo-generated current, so that the detector has higher photosensitivity. The ZnO material has higher stability because of the excellent physical and chemical properties of the device, and is one of the materials most suitable for industrial integration application at present.
Although there is a great progress in the research of zinc oxide nanomaterial at present, there is still much room for development. According to the analysis, the invention provides a method for preparing a nanowire array device from bottom to top by Ti-assisted directional growth, znO nanowires with good crystallization quality are simply and easily obtained in one step under the action of a Ti/Au catalytic layer by a CVD method, heterojunction is obtained by directly contacting Si, secondary treatment is avoided, and finally the nanowire array device is obtained.
Disclosure of Invention
According to the basic problems, a layer of metal Ti is added to assist directional growth to prepare a nanowire array device from bottom to top, and the principle and the function of the Ti layer are as follows: the Ti layer is first siliconized due to the high temperature environment during the growth of the nanowires by CVD method-the Si sheet naturally forms an extremely thin oxide layer (SiO) 2 ) Is diffused into the Ti layer at high temperature to be decomposed, and finally TiSi2 is formed. This process results in the SiO2 layer being consumed by the reaction and also in the direct contact of Au with Si to form Au-Si bonds. The addition of the Ti layer enhances the binding force of Au and the Si substrate, and can be combined with a VLS mechanism generated in the growth of a CVD method, and the addition of the Ti layer slows down the process of forming liquid drops by Au melting, and provides force in the direction vertical to the substrate at the initial stage of nanowire nucleation, thereby promoting the directional growth of the ZnO nanowire array in the vertical direction. Meanwhile, the bonding force between the Au and the Si substrate is enhanced by the Ti, so that the Au layer is not easy to fall off from the Si sheet, different Au patterns can be obtained by photoetching and other processes on the Si substrate, and the growth of the nanowire can be applied to the requirements of different devices in future research.
The invention provides a Ti-assisted directional growth device for preparing a nanowire array from bottom to top, which has the following structure:
an n-ZnO nanowire array of a vertical substrate is grown on the p-Si substrate, and the thickness of the n-ZnO nanowire array is 3-8 mu m.
Different photoetching plates can be selected according to different pattern requirements, and finally ZnO nanowire arrays with different patterns are obtained.
And supporting the nanowire layer by using a PDMS electrode material, and then coating silver paste on the top end point of the ZnO nanowire to finally obtain the Ag/n-ZnO/p-Si/Ag heterojunction.
A preparation method for preparing a nanowire array device by Ti-assisted directional growth from bottom to top comprises the following steps:
step 1: preparing a p-Si sheet substrate, and cleaning the substrate;
step 2: patterning the substrate by using a mask plate through a photolithography process;
step 3: etching the photoresist-free part of the substrate to obtain square pit arrays with the depth of 1-3 mu m, and sequentially sputtering a metal layer Ti of about 1-5 nm and Au of 5-15 nm from bottom to top in the pits to obtain patterned Ti/Au catalyst arrays;
step 4: removing the photoresist by using a stripping process;
step 5: placing the substrate sputtered with Ti and Au in the pit into a high-temperature tube furnace;
step 6: weighing medicines required by growing the nanowires on an electronic scale;
step 7: placing the medicines into a corundum boat, and placing the medicines into a position 20cm away from a high-temperature tube furnace;
step 8: starting a high-temperature tube furnace to grow ZnO nanowires by a CVD method;
step 9: after the growth is finished, the high-temperature tube furnace and the vacuum pump are closed, so that the temperature of the high-temperature tube furnace and the vacuum pump is naturally reduced, and then a sample is taken out;
step 10: filling small pits in which ZnO nanowires grow by sucking a small amount of mixed solution of PDMS and a curing agent (volume ratio is 10:1) through a needle tube, and drying for 10min at 150 ℃ so as to support the nanowires and facilitate the subsequent preparation of electrodes;
step 11: preparing an electrode, namely taking a small amount of silver paste to be respectively dotted on the top end of the nanowire and the substrate beside the nanowire, and drying the electrode at 150 ℃ for 10min.
The step 1 comprises the following steps:
1-a: putting the Si sheet into a clean glass beaker, adding acetone, boiling for 3-5min, and pouring out twice;
1-b: adding absolute ethyl alcohol, boiling for 3-5min, and operating twice;
1-c: deionized water is used for cleaning for about 5min, and then nitrogen is used for drying;
the step 2 comprises the following steps:
2-a: placing the clean substrate on a heating table for drying for 3min;
2-b: spin coating 5214 photoresist on the front surface, baking for 50s, exposing, developing and photoresist, and photoetching a small pit array with a required pattern on the front surface by using a photoetching process and a mask plate;
the medicines in the step 6 are pure ZnO powder (99.999-100 meshes);
the step 8 includes: the first heating stage is that the heating speed is 20 ℃/min, the temperature reaches 1400 ℃, the pressure is kept to be 9.4e4pa, and the Ar gas flow is kept to be 50sccm; in the second growth stage, the temperature is kept at 1400 ℃ for 30min, the pressure is regulated, and 380-700pa is kept; and in the stage three, cooling, naturally cooling the high-temperature tube furnace to room temperature, and taking out the sample wafer.
The invention provides a method for preparing a nanowire array device from bottom to top by Ti-assisted directional growth, which has the advantages that: the growth direction of the nanowire is more controllable, compared with the randomness of the growth direction of the ZnO nanowire which is grown without adding the Ti layer, the growth direction of the nanowire is more controllable and vertical to the substrate after adding the Ti, and the preparation of the device is facilitated. Meanwhile, under the condition that other growth conditions are kept the same, the length and the diameter of the nanowire are also changed after Ti layers with different thicknesses are added, the larger the diameter of the nanowire which grows thicker in the range of 1-5 nm is, the larger the diameter of the nanowire is, the larger the diameter is, the about 50-300 nm is, and the length is about 3-8 mu m, so that the nanowire with smaller length-diameter ratio can be selected from the nanowire, the higher the quality is, and the nanowire can be reused for a device.
Drawings
FIG. 1 is a schematic diagram showing the variation of Ti/Au catalytic layer at high temperature in a tube furnace in the present invention;
FIG. 2 is a flow chart of an embodiment of the present invention; a. a Si substrate; b. a photoresist; c. a mask; d. ti; e. au; f. ZnO nanowires; g. PDMS; h. ag.
FIG. 3 is a graph of pressure, temperature, gas flow and time for growth by CVD method according to the present invention; wherein (1) is a pressure versus time profile; (2) is a temperature versus time profile; (3) a gas flow rate versus time profile;
the first heating stage is that the heating speed is 20 ℃/min, the temperature reaches 1400 ℃, the pressure is kept to be 9.4e4pa, and the Ar gas flow is kept to be 50sccm; in the second growth stage, the temperature is kept at 1400 ℃, the pressure is regulated to 380-700pa, and the growth is carried out for 30min; a third cooling stage, wherein the high-temperature tube furnace naturally cools to room temperature;
fig. 4 (a) shows a SEM image of disordered ZnO nanowires grown without Ti layer (b) showing ZnO nanowires relatively aligned after Ti layer addition;
FIG. 5 is a side view SEM of a ZnO nanowire grown after addition of a Ti layer;
fig. 6 is an SEM image of patterned ZnO nanowires grown according to an embodiment of the present invention.
Detailed description of the preferred embodiments
In order to make the operation flow of the present invention clearer, a method for preparing a nanowire array device from bottom to top by Ti-assisted directional growth according to the present invention will be described in detail with reference to the accompanying drawings and the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Cutting the p-Si sheet into small pieces with the length of 1cm multiplied by 1cm, cleaning the small pieces with acetone, absolute ethyl alcohol and deionized water, and drying the small pieces with nitrogen;
(2) Placing the substrate in the step (1) on a heating table to be dried for 3min;
(3) Placing the substrate of the step (2) on a spin coater, spin-coating 5214 photoresist on the front surface, post-baking for 50s, exposing, developing and photoresist-coating, and photoetching 100 μm on the front surface by using a mask plate
A x 100 μm pattern array;
(4) Etching the substrate with the patterns photoetched in the step (3) to obtain a corresponding 3 mu m deep pit array, and then putting the corresponding 3 mu m deep pit array into an inlet sputtering machine to sputter a Ti layer and an Au layer, wherein the sputtered metal layer is Ti1nm and Au5nm;
(5) Placing the sputtered sample in the step (4) into stripping liquid for ultrasonic treatment for 150s to strip residual photoresist, and then placing the residual photoresist into a corundum boat;
(6) Weighing pure ZnO powder (99.999-100 meshes) by an electronic scale, and putting about 1.5g into a corundum boat;
(7) Placing the corundum boat with the substrate placed in the step (5) at a position 20cm away from the center of the tubular furnace, and placing the corundum boat with the source material placed in the step (6) into the center of the tubular furnace;
(8) Opening circulating water to prepare for furnace tube temperature rise and fall;
(9) Heating up to 1400 ℃ at 20 ℃/min by setting a high-temperature tube furnace, and adjusting and maintaining the pressure intensity
9.4e4pa, ar gas flow was kept at 50sccm; in the growth stage, the temperature is kept at 1400 ℃, the pressure is regulated to 700pa, and the growth is carried out for 30min;
(10) After 30min, the growth time is ended, and after the temperature is automatically reduced to room temperature, the sample is taken out, so that a heterojunction based on p-Si/n-ZnO is obtained;
(11) The ZnO nanowire grown by using a scanning electron microscope is more orderly vertical to the Si substrate, the diameter is about 60nm, the length is about 5 mu m, and the length-diameter ratio reaches 83.3
(the nanowires of the invention are tapered and aligned relative to the absence of Ti).
(12) Preparing an electrode, wherein the volume ratio of the preparation is 10:1, sucking a small amount of mixed solution of PDMS and a curing agent by using a needle tube, injecting the small amount of mixed solution into a pit, and drying the small pit at 150 ℃ for 10min;
(13) And dipping a small amount of silver paste points on the Si substrate at the top end of the nanowire and beside the nanowire to obtain the Ag/n-ZnO/p-Si/Ag heterojunction.

Claims (9)

1. A Ti-assisted directional growth is used for preparing a nanowire array device from bottom to top, and is characterized by comprising the following structures:
an n-ZnO nanowire array vertical to the substrate is grown on the p-Si substrate, and the thickness of the n-ZnO nanowire array is 5-15 mu m;
and selecting different photoetching plates according to different pattern requirements to finally obtain ZnO nanowire arrays with different patterns.
2. The method for preparing the nanowire array device from bottom to top by Ti-assisted directional growth according to claim 1, wherein a PDMS electrode material is selected to support the nanowire layer, and then silver paste is applied to the top end point of the ZnO nanowire, so that the Ag/n-ZnO/p-Si/Ag heterojunction is finally obtained.
3. The method for preparing the nanowire array device by Ti-assisted directional growth from bottom to top according to claim 1, comprising the following steps:
step 1: preparing a p-Si sheet substrate, and cleaning the substrate;
step 2: patterning the substrate by using a mask plate through a photolithography process;
step 3: etching the photoresist-free part of the substrate to obtain a plurality of pit arrays with the depth of 1-3 mu m, and sequentially sputtering a metal layer Ti of about 1-5 nm and Au of 5-15 nm from bottom to top in the pits to obtain a patterned Ti/Au catalyst array;
step 4: removing the photoresist by using a stripping process;
step 5: placing the substrate sputtered with Ti and Au in the pit into a high-temperature tube furnace;
step 6: weighing medicines required by growing the nanowires on an electronic scale;
step 7: placing the medicines into a corundum boat, and placing the medicines into a position 20cm away from a high-temperature tube furnace;
step 8: starting a high-temperature tube furnace to grow ZnO nanowires by a CVD method;
step 9: after the growth is finished, the high-temperature tube furnace and the vacuum pump are closed, so that the temperature of the high-temperature tube furnace and the vacuum pump is naturally reduced, and then a sample is taken out;
step 10: filling small pits for growing ZnO nanowires by sucking a small amount of mixed solution of PDMS and a curing agent (volume ratio is 10:1) through a needle tube, and drying at 150 DEG C
For 10min, so as to support the nanowire and facilitate the subsequent preparation of the electrode;
step 11: preparing an electrode, namely taking a small amount of silver paste to be respectively dotted on the top end of the nanowire and the substrate beside the nanowire, and drying the electrode at 150 ℃ for 10min.
4. A method according to claim 3, wherein said step 1 comprises:
1-a: putting the Si sheet into a clean glass beaker, adding acetone, boiling for 3-5min, and pouring out twice;
1-b: adding absolute ethyl alcohol, boiling for 3-5min, and operating twice;
1-c: the deionized water is washed for about 5min, and then is dried by nitrogen.
5. A method according to claim 3, wherein said step 2 comprises:
2-a: placing the clean substrate on a heating table for drying for 3min;
2-b: the photoresist is coated on the front side in a spin mode 5214, and after the photoresist is baked for 50 seconds, exposed, developed and beaten, a small pit array with a required pattern is formed on the front side by photoetching technology and a mask plate in a photoetching mode.
6. A method according to claim 3, wherein the pharmaceutical product in step 6 is pure ZnO powder (99.999% -100 mesh).
7. A method according to claim 3, wherein said step 8 comprises: the first heating stage is that the heating speed is 20 ℃/min, the temperature reaches 1400 ℃, the pressure is kept to be 9.4e4pa, and the Ar gas flow is kept to be 50sccm; in the second growth stage, the temperature is kept at 1400 ℃ for 30min, the pressure is regulated, and 380-700pa is kept; and in the stage three, cooling, naturally cooling the high-temperature tube furnace to room temperature, and taking out the sample wafer.
8. A method according to claim 3, wherein more than 1 nanowire is grown in each pit.
9. A method according to claim 3, wherein the addition of the Ti layer provides a force in a direction perpendicular to the substrate at the beginning of nanowire nucleation to promote directional growth of the ZnO nanowire array in a vertical direction, and the resulting ZnO nanowires contact Si to form a heterojunction, resulting in a self-powered uv detector.
CN202310127810.2A 2023-02-08 2023-02-08 Method for preparing nanowire array device from bottom to top through Ti-assisted directional growth Pending CN116190490A (en)

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