CN113461999B - Method for preparing two-dimensional noble metal micro-nano pattern large-scale array - Google Patents

Method for preparing two-dimensional noble metal micro-nano pattern large-scale array Download PDF

Info

Publication number
CN113461999B
CN113461999B CN202110655144.0A CN202110655144A CN113461999B CN 113461999 B CN113461999 B CN 113461999B CN 202110655144 A CN202110655144 A CN 202110655144A CN 113461999 B CN113461999 B CN 113461999B
Authority
CN
China
Prior art keywords
peo
p2vp
hot
array
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110655144.0A
Other languages
Chinese (zh)
Other versions
CN113461999A (en
Inventor
陈静波
张彬
王兴昱
王冰花
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Original Assignee
Zhengzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University filed Critical Zhengzhou University
Publication of CN113461999A publication Critical patent/CN113461999A/en
Application granted granted Critical
Publication of CN113461999B publication Critical patent/CN113461999B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Abstract

The invention belongs to the technical field of micro-nano processing, and particularly relates to a method for preparing a two-dimensional noble metal micro-nano pattern large-scale array. The method is realized by spin coating polyethylene oxide-bPoly-2-vinylpyridine (PEO-b-P2 VP) solution to prepare a film. And (3) hot-pressing the film by adopting the PDMS soft template, and changing the hot-pressing temperature and the hot-pressing pressure to obtain the crystal pattern arrays with different widths. The size and the position of the crystallization pattern array can be regulated and controlled through selective melting and dissolution, and finally, a proper precursor is selected to perform a complex reaction with P2VP to obtain the noble metal pattern array. The construction method realizes the regulation and control of the size and the position of the noble metal pattern on a micro-nano scale. The constructed noble metal pattern array has good conductivity, and is expected to expand the application of the noble metal pattern array in the fields of sensors, energy sources and the like.

Description

Method for preparing two-dimensional noble metal micro-nano pattern large-scale array
Technical Field
The invention belongs to the technical field of micro-nano processing, and particularly relates to a method for preparing a two-dimensional noble metal micro-nano pattern large-scale array.
Background
The noble metal micro-nano pattern has the characteristics of high conductivity, surface plasmon resonance effect, excellent catalytic activity and the like, and is increasingly widely researched and applied in the fields of nano photoelectric devices, surface enhanced spectroscopy, biosensors and the like. Compared with disordered micro-nano noble metal patterns, the quantum effect of the array pattern is more prominent, so that the array pattern has more excellent performance. At present, most solar cells are covered with a layer of noble metal pattern array on the surface by methods such as a spin coating method or a deposition method, however, the array form is mostly concentrated on several specific pattern arrays such as a line array, a ball array and a dot array, and the two-dimensional noble metal pattern array is rarely reported.
Although two-dimensional micro-nano noble metal patterns can be obtained by a block copolymer crystallization template method, the regulation of the shape, size and especially position of the two-dimensional noble metal patterns is still a challenging subject. In recent years, PDMS soft templates have been used to study the crystallization behavior of block copolymer films under the constraint of micro-nano lateral morphology and scale. However, the application is mostly related to the conformal pattern, i.e. the polymer is imprinted and the anti-etching layer is present. In order to regulate the position of the polymer crystal, the anti-etching layer needs to be completely removed, so how to regulate the position of the crystal by using the PDMS soft template is not solved.
Disclosure of Invention
The invention provides a method for preparing a large-scale two-dimensional noble metal micro-nano pattern array, which comprises the steps of firstly spin-coating polyoxyethylene-bPoly-2-vinylpyridine (PEO-b-P2 VP) solution, and hot-pressing the film by adopting a PDMS soft template, and changing the hot-pressing temperature and the hot-pressing pressure to obtain the crystal pattern arrays with different widths. Then further constructing PEO-with controllable size and position by selective melting and dissolvingb-P2VP crystallization pattern array, and finally, preparing the gold particle pattern array by carrying out complex reaction on the gold ions and the P2 VP. The method realizes the regulation and control of the size and the position of the noble metal pattern on the micro-nano scale. The invention can be used in practice for solar cells, nano-optoelectronic device designs and sensors.
The technical scheme of the invention is as follows:
a method for preparing a large-scale two-dimensional noble metal micro-nano pattern array comprises the following steps:
step 1: the block copolymer PEO-b-P2VP as a raw material is completely dissolved in a solvent to prepare a solution;
step 2: PEO-b-the P2 VP/tolumene solution is heated on a hot plate for several hours until the solute is sufficiently dissolved;
and 3, step 3: preparing an ultrathin film by using a spin coater with a silicon wafer subjected to surface treatment as a substrate;
and 4, step 4: ultrasonically cleaning the surface of the PDMS template by using acetone, alcohol and water in sequence;
and 5: PEO-b-the P2VP ultrathin film sample is placed on a hot stage and heated to remove the thermal history of the ultrathin film;
and 6: placing the clean PDMS soft template in PEO-b-P2VP ultrathin membrane, then placing weights with different masses on a soft template, and hot-pressing for a period of time;
and 7: after the hot pressing is finished, the pressure is removed, and the PEO-bTaking the P2VP sample from the PDMS template, finally placing the sample on an aluminum plate, quenching to room temperature, and carrying out isothermal crystallization to obtain the striped PEO-bThe P2VP crystallization pattern array, the hot pressing and the isothermal crystallization regulate and control PEO-b-the position of the P2VP crystallization pattern array;
and 8: further regulation of PEO-b-position, size and morphology of the P2VP crystalline pattern array;
and step 9: washing away PEO-b-cryocrystals around the P2VP crystallization template, the morphology and size of which are controlled;
step 10: and preparing a gold particle pattern array by carrying out a complex reaction between gold ions and P2 VP.
In a further embodiment, the PEO-used in step 1bP2VP having a number average molecular weight of 4000-2000g/mol, dissolved PEO-bThe solvent of the P2VP is toluene, and the mass fraction of the solute of the mixed solution is 0.5 wt-%.
In a further embodiment, the prepared mixed solution is heated in a hot stage at 105 ℃ for 3 hours to fully dissolve the solute as described in step 2.
In a further embodiment, the hydrophilic substrate in step 3 is obtained by treating the substrate with ultraviolet ozone, wherein the power of the ultraviolet lamp is 30 w and the treatment time is 30 min.
In a further scheme, the spinning conditions of the spin coater in the step 3 are as follows: the ultrathin film was prepared by spinning at 4000 rpm for 120s under the protection of a nitrogen atmosphere.
In a further embodiment, the step 4 of cleaning the surface of the PDMS template is performed according to the following method: and (3) putting the template into acetone, performing ultrasonic treatment for 7-10 min, putting the template into ethanol, performing ultrasonic treatment for 7-10 min, then putting the template into deionized water, performing ultrasonic treatment for 7-10 min, and finally blowing the residual liquid on the surface of the PDMS template by using high-purity nitrogen.
In a further embodiment, the step 5 of eliminating the thermal history of the film specifically includes: use of hot stage to treat PEO-bHeating the-P2 VP ultrathin film to 60-110 ℃, and preserving heat for 10min. The optimum heating temperature is 90 ℃.
In a further embodiment, the hot pressing in step 6 specifically includes: PEO-bHeating the-P2 VP ultrathin membrane to 60-110 ℃, applying pressure of 0.2-1.5 bar, and maintaining the pressure of 10 s.
In a further embodiment, the isothermal crystallization in step 7 is specifically: the PEO obtained in the step 6bthe-P2 VP hot-pressed film is placed on a LinKam hot table, and under the nitrogen protective atmosphere, the PEO-bthe-P2 VP film is placed at 24 ℃ for isothermal crystallization for 24h to obtain the striped PEO-b-P2VP dendrites.
In a further embodiment, the selective melting in step 8 is specifically: the striped PEO-bAnd (3) placing the P2VP dendrite on a LinKam hot table, heating from 24 ℃ to 47-48 ℃ at a heating rate of 1-5 ℃/min under the nitrogen protection atmosphere, preserving heat at the partial melting temperature for 3min, then cooling from the partial melting temperature to 42 ℃ at a cooling rate of 5 ℃/min, and carrying out isothermal crystallization at 42 ℃ for 3 min.
In a further embodiment, the selective dissolution method described in step 9 comprises the steps of: taking a 10 ℃ toluene solvent, directly dripping the toluene solvent on the surface of a crystal sample on a spin coater, after the solvent is fully contacted with the sample for 1-3 s, starting the spin coater, rotating 120s at 5000 rpm, and after the spin coating is finished, blowing off the residual solvent on the surface of the sample by using high-purity nitrogen.
In a further embodiment, the process of the complexation reaction between the gold ions and the P2VP in step 10 is: and immersing the completely washed sample in a 1.0% chloroauric acid/n-octanol solution, keeping the sample in the dark for 24 hours to ensure the sufficient loading of the gold ions, and then repeatedly washing the sample by using an n-octanol pure solvent to wash off the gold particles deposited on the surface of the silicon wafer without loading.
In a further scheme, the sample loaded with gold ions in the step 10 is cleaned by a plasma cleaning machine, wherein the cleaning parameters are as follows: the gas is air, the flow rate is 20sccm, the power is 80w, and the time is 5min.
The invention has the beneficial effects that:
the method is based on the combination of polymer film crystallization and PDMS soft template hot pressing to construct a noble metal pattern array, and the method utilizes the difference of the stability of folded chain lamella crystals obtained in the crystallization process of macromolecules in an ultra-thin film and combines the PDMS soft template hot pressing to realize the control of the position, the shape and the size of a block copolymer crystallization pattern array on a micro-nano scale. The method has the advantages of small heat loss and high utilization rate of the soft template in the process of constructing the two-dimensional noble metal pattern array.
The precious metal pattern arrays reported at present are mainly specific pattern arrays such as nanowire arrays, spherical or hemispherical arrays and dot arrays, or two-dimensional precious metal patterns distributed in a disordered manner.
In addition, the previously reported use method of the PDMS soft template is mostly used for transferring a pattern to a bottom layer polymer to realize the copying of the pattern, and in the invention, the position of a polymer material in the ultrathin film is regulated and controlled by using the PDMS soft template to finally realize the regulation and control of the position of the noble metal pattern, so that the noble metal pattern array is prepared.
The method for regulating and controlling the metal pattern array has the advantages of simple preparation process, convenient operation and less working procedures required by hot pressing; the pressure used by the hot pressing process is small, and the loss to the template is small, so that the soft template can be used for a longer service life; in addition, the template does not need to be in contact with the material for a long time to promote nucleation, the primary crystallization process of the material can be completed at room temperature (24 ℃), and the post-treatment (selective melting and selective dissolution) is also performed at 50 ℃ lower, so that the energy consumption is reduced; the finally prepared two-dimensional noble metal pattern array has important research and application prospects in the aspects of photoelectronic devices, surface enhanced spectroscopy, biomedical materials, sensor development and the like, and has better social and economic benefits.
Drawings
FIG. 1 is a schematic diagram of a process for preparing PEO-bSchematic flow chart of constructing gold particle pattern array by adopting PDMS soft template in P2VP ultrathin membrane.
FIG. 2 is a schematic diagram of a process for preparing PEO-bIsothermal crystallization to PEO-b-atomic force microscopy pictures of P2VP platelet arrays.
FIG. 3 is a schematic diagram of a process for preparing PEO-bIsothermal crystallization into PEO-b-atomic force microscopy pictures of P2VP platelet arrays.
FIG. 4 is a drawing of initial PEO-bHeating up the P2VP stripe-shaped platelet to partially melt at different heating rates and cooling down for crystallization to form PEO-b-atomic force microscopy characterization of P2VP crystalline array patterns.
FIG. 5 is PEO-bAtomic force microscopy pictures of regular crystals of-P2 VP ultrathin film crystallized isothermally at 43 ℃ for 40min dissolved in toluene at 10 ℃ for various times.
FIG. 6 is a drawing of initial PEO-bHeating up the P2VP stripe-shaped platelet to partially melt and cooling down for crystallization, and then dissolving for different times to form PEO-b-atomic force microscopy characterization of P2VP crystalline array patterns.
FIG. 7 is a drawing of initial PEO-bHeating P2VP strip-shaped platelets to different partial melting temperatures, and cooling for crystallization to form PEO-b-atomic force microscopy characterization of the P2VP crystalline array pattern and the corresponding gold particle pattern array.
FIG. 8 is a graph of atomic force conductivity test results for an array of gold particle patterns.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, which are provided for understanding the technical solutions of the present invention, but are not intended to limit the scope of the present invention.
PEO-bThe P2 VPs are all available from Polymer Source, canada, molecular weights of 4000-2000g/mol, and the PEO block has a backbone structure of-CH2-CH2-O-, has good flexibility, is easily crystallized, has a number average molecular weight of 4000 g/mol and a glass transition temperature of about-67 ℃; the number average molecular weight of the P2VP amorphous block is 2000g/mol,T gabout 87 deg.c. The silicon wafer is a P100 silicon wafer produced by Zhejiang Lijing photoelectricity technology Limited. The film spinning instrument is KW-4A type produced by microelectronic research institute of Chinese academy of sciences. The polarization microscope (POM) used was of the type: the model of a corresponding matched hot platform of the Olympus BX-61 is as follows: linkam LTS420. The Atomic Force Microscope (AFM) used was purchased from Bruker, USA, and the model number is: icon, the ellipsometer used is alpha-SE from j.a.woollam co. Usa.
Example 1 Hot pressing temperature vs. PEO-b-Effect of P2VP Crystal Pattern array
PEO production by spin coating-b-P2VP ultrathin film: firstly, wrapping a sample bottle and a cover with the specification of 6mL by using an aluminum foil and blowing clean by using high-purity nitrogen; followed by PEO-b-P2VP (4000-2000 g/mol) and toluene (analytically pure) were brought to a concentration of 0.5 wt-%; the solution was then heated on a hot plate at 105 ℃ for 3h with constant stirring until the solute was fully dissolved. Then, the cleaned silicon wafer was placed in a spin coater (model: KW-4A, available from the institute of microelectronics, national academy of sciences) to obtain 16. Mu.L of PEO-b-Spin coating P2VP solution in the center of silicon wafer for 120s by centrifugal force on a spin coater to obtain PEO with film thickness of 14.5nm-b-P2VP ultrathin film, as shown in FIG. 1a.
Then the ultrathin film is placed on a hot table and heated to different hot pressing temperatures (T p) Keeping the temperature at 60-110 ℃ for 10min; placing PDMS soft template on PEO with 1bar hot pressing pressure-b-On the P2VP ultrathin membrane (figure 1 b), after the pressure is maintained for 10s, the material is extruded into the cavity layer of the PDMS soft template; will be hot pressedPost PEO-bThe P2VP sample was placed on an aluminum plate and quenched to room temperature (demold temperature); the pressure was then released and the PDMS soft template was pulled from the PEO-b-The P2VP ultrathin film was removed. The specific hot pressing flow diagram is shown in FIGS. 1 b-c. The prepared PEO was then-b-And (3) crystallizing the P2VP ultrathin film sample for 24 hours at 24 ℃ in an inert gas nitrogen protection atmosphere for later use.
From FIG. 1c and FIGS. 2a-f it can be seen that: no material is present above the silicon substrate hot pressed by the soft template bumps.
FIGS. 2a-f are graphs showing the results of PEO-bDifferent autoclave temperatures in P2VP autoclave films (T p) Crystallization into PEO-ion-doped material at the temperature of 60-110 DEG Cb-atomic force microscopy pictures of P2VP crystalline pattern arrays. From the results shown in FIGS. 2a-f, it can be seen that as the hot pressing temperature increases, PEO in the hot pressed film-b-The width of P2VP lamella is reduced, so that the PEO can be regulated and controlled by regulating and controlling the hot pressing temperature-b-Position of P2VP crystal pattern array. When in useT pAnd when the temperature is not less than 90 ℃, the width of the obtained platelet at the hot pressing temperature is consistent with that of the soft template cavity layer.
Example 2 Hot pressing pressure on PEO-b-Effect of P2VP Crystal Pattern array
The film thickness was 14.5nm for PEO-b-Placing the P2VP ultrathin film on a hot bench, heating to 90 deg.C, and hot-pressingT p) Preserving the heat for 10min; placing the PDMS soft template into PEO at a hot pressing pressure of 0.2 bar-1.5 bar-b-On the P2VP ultrathin film, maintaining the pressure for 10s to ensure that the material is extruded into the cavity layer of the PDMS soft template; the PEO after hot pressingbThe P2VP sample was placed on an aluminum plate and quenched to room temperature (demold temperature); the pressure was then released and the PDMS soft template was pulled from the PEO-b-The P2VP ultrathin film was removed.
From the results shown in FIGS. 3 a-e: no material is present above the silicon substrate hot pressed by the soft template bumps. And PEO in the hot-pressed film increases along with the increase of the hot-pressing pressure-b-The width of P2VP lamella is reduced, so that the PEO can be regulated and controlled by regulating and controlling the hot-pressing pressure-b-Position of P2VP crystal pattern array. When the temperature is higher than the set temperaturePAnd when the pressure is not less than 1bar, the width of the obtained platelet under the hot pressing pressure is consistent with that of the cavity layer of the soft template.
Example 3 temperature ramp Rate for Selective melting on PEO-b-Effect of P2VP Crystal Pattern array
Under the protection of nitrogen, the hot pressing condition is thatT p = 90℃，PPEO = 1bar-b-The P2VP hot-pressed film is placed at 24 ℃ for isothermal crystallization of 24h to obtain initial crystals in a stripe shape as shown in FIG. 2 d; then at different ramp rates (V) From 24 ℃ to the partial melting temperature at rates of 1 ℃/min, 2 ℃/min and 5 ℃/min ((ii))T s) Keeping the temperature at 47 ℃ for 3min; then reducing the temperature to 42 ℃ at a cooling rate of 5 ℃/min, and carrying out isothermal crystallization for 3min; the sample was quickly removed and placed on an aluminum plate to quench to room temperature.
From the results shown in FIGS. 4a-c, it can be seen that PEO increases with the rate of temperature increase for selective melting-b-The nucleation density of the P2VP crystals is reduced, and the crystals are intensively distributed at the central position of the strip-shaped template and are arranged in a linear shape, the distribution range of the crystals is reduced from 15 mu m to 10 mu m and 5 mu m, and the positions are marked by white dotted lines in figures 4 a-c; this is because when the melt ramp rate is increased, the PEO-b-The low-temperature crystals on the two sides of the P2VP stripe crystals melt without thickening, and the central position with better stability is reserved to form a linear crystal pattern array. Therefore, PEO in hot-pressed films can be regulated and controlled by changing the melting temperature rise rate-b-Distribution position of P2VP crystal pattern array.
Example 4 dissolution time for Selective dissolution on PEO in ultrathin films-b-Effect of P2VP regular Crystal morphology and size
Under the protection of nitrogen, 14.5nm of PEO-b-placing the P2VP ultrathin film at 24 ℃ for isothermal crystallization of 24h to obtain regular initial crystals as shown in FIG. 5 a; then toluene with 10 ℃ is used for dissolving for 2s to 16s, and the PEO is regulated-b-Size and morphology of P2VP crystals.
As can be seen from the results shown in FIG. 5, as the dissolution time was prolonged, PEO was attributed to-b-The (100) crystal plane of P2VP dissolves at a faster rate than the (120) crystal plane, so that the morphology is changed from the first square shape to the octagon shape, then to the hexagon shape, and finally to the approximately rectangular shape, and the size is reduced from the micrometer scale to the nanometer scale. Thus, PEO in ultrathin films can be tailored by selective dissolution-b-Morphology and size of the P2VP crystal pattern.
Example 5 dissolution number for Selective dissolution vs. PEO-b-Effect of P2VP Crystal Pattern array
Under the protection of nitrogen, the hot pressing condition is as followsT p = 90℃，PPEO = 1bar-b-Placing the P2VP hot-pressed film at 24 ℃ for isothermal crystallization of 24h to obtain stripe-shaped initial crystals as shown in FIG. 2 d; then heating from 24 ℃ to 47 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 3min; then reducing the temperature to 42 ℃ at the cooling rate of 5 ℃/min, and carrying out isothermal crystallization for 3min; the sample was quickly removed and placed on an aluminum plate to quench to room temperature. PEO was then controlled by dissolving once to twice with 16. Mu.L of toluene at 10 ℃-b-Size and morphology of the P2VP crystal array pattern.
As can be seen from the results shown in FIG. 6, PEO was dissolved more frequently-b-The average size of the P2VP platelets gradually decreases with increasing number of solubilizations. Thus, PEO in hot-pressed films can be controlled by selective dissolution-b-Morphology and size of the P2VP crystal pattern.
Example 6 partial melting temperature vs. PEO for Selective melting-b-Effect of P2VP Crystal Pattern array
Under the protection of nitrogen, the hot pressing condition is thatT p = 90℃，PPEO = 1bar-b-The P2VP hot-pressed film is placed at 24 ℃ for isothermal crystallization of 24h to obtain initial crystals in a stripe shape as shown in FIG. 2 d; from 24 ℃ to the partial melting temperature at a ramp rate of 1 ℃/min (ii)T s) Keeping the temperature at 47 deg.C, 47.5 deg.C and 48 deg.C for 3min; then reducing the temperature to 42 ℃ at the cooling rate of 5 ℃/min, and carrying out isothermal crystallization for 3min; the sample was quickly removed and placed on an aluminum plate to quench to room temperature. To obtain PEO-b-An array of P2VP crystallization templates, as shown in fig. 7 a-c. Next, gold particle arrays were prepared by mounting them, as shown in FIGS. 1 d-f.
FIGS. 7d-f are PEO's of FIGS. 7a-c-b-The P2VP crystallization template array is a gold particle pattern array prepared by carrying gold ions.
As can be seen from the results shown in FIG. 7, PEO increased with the increase of the partial melting temperature-b-The nucleation density of the P2VP crystals is reduced and gradually and intensively distributedThe central position of the strip-shaped template can be obtained by loading gold ions and PEO-b-A gold particle pattern array consistent with the P2VP crystallization template array; therefore, the distribution position of the two-dimensional gold particle pattern can be regulated by changing the partial melting temperature.
Example 7 conductivity testing of two-dimensional gold particle pattern arrays
Under the protection of nitrogen, the hot pressing condition is as followsT p = 90℃，PPEO = 1bar-b-Placing the P2VP hot-pressed film at 24 ℃ for isothermal crystallization of 24h to obtain stripe-shaped initial crystals as shown in FIG. 2 d; heating from 24 deg.C to 47 deg.C at a rate of 1 deg.C/min, and holding for 3min; then reducing the temperature to 42 ℃ at a cooling rate of 5 ℃/min, and carrying out isothermal crystallization for 3min; the sample was quickly removed and placed on an aluminum plate to quench to room temperature. And finally, preparing the gold particle pattern array by using a P2VP block complex alloy ion combination sintering process. Fig. 8a corresponds to a partial enlarged view of fig. 7e within the white dashed box of the gold particle pattern array. FIGS. 8b and c are graphs corresponding to the PF-TUNA mode conductivity test results of the conductive atomic force microscope, the average current graph and the highest current graph, respectively.
The experimental results show that: PEO-based-b-The two-dimensional gold particle pattern array prepared by the P2VP crystal array template has good conductivity, the average current reaches 500 fA, the highest current reaches 10 pA, and the conductivity is distributed uniformly.
The above-described embodiments are merely preferred embodiments of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications in the structure, features and principles described in the present invention should be included in the claims of the present invention.

Claims (6)

1. A method for preparing a two-dimensional noble metal micro-nano pattern large-scale array is characterized by comprising the following steps:
first preparing PEO-b-P2VP ultrathin film, followed by heating to eliminate the thermal history of the ultrathin film;
placing the PDMS soft template in PEO-b-P2VP ultra-thin film, maintaining pressure to extrude the material into the cavity layer of PDMS soft templateWhen the soft template is hot pressed, PEO ion-free layer is not arranged above the silicon substratebPresence of P2VP material, subsequent PEO-b-quenching the P2VP sample to room temperature; the pressure was then released and the PDMS soft template was removed from the PEO-b-removing the P2VP to obtain a hot-pressed film;
subsequently preparing PEO-ion-doped silicon oxide (PEO) by isothermal crystallization of hot-pressed filmb-a P2VP crystalline array pattern; the isothermal crystallization is as follows: placing the hot-pressed film at 24 ℃ for isothermal crystallization of 24h to obtain initial crystals in a stripe shape;
then regulating and controlling PEO (polyethylene oxide) through selective melting and selective dissolutionb-a P2VP crystalline array pattern; the selective melting is the melting of PEO-b-P2VP crystal array pattern heating part melting and cooling crystallization; the partial melting and cooling crystallization specifically comprises the following steps: PEO-bThe P2VP crystallization pattern array pattern is placed on a hot table, the temperature is raised from 24 ℃ to 47-48 ℃ of partial melting temperature at the temperature raising rate of 1-5 ℃/min under the nitrogen protection atmosphere, the temperature is kept for 3min at the partial melting temperature, then the temperature is lowered from the partial melting temperature to 42 ℃ at the temperature lowering rate of 5 ℃/min, and isothermal crystallization is carried out for 3min at the temperature of 42 ℃;
and finally, carrying out a complex reaction on the gold ions and the P2VP to prepare a gold particle pattern array.
2. The method for preparing a large-scale two-dimensional precious metal micro-nano pattern array according to claim 1, wherein the PDMS soft template is hot-pressed with PEO-bIn the process of preparing the-P2 VP film, the hot pressing temperature is 60-110 ℃.
3. The method for preparing a large-scale two-dimensional precious metal micro-nano pattern array according to claim 1, wherein the PDMS soft template is hot-pressed with PEO-bAnd in the process of preparing the P2VP film, the hot-pressing pressure is 0.2 bar-1.5 bar.
4. The method for preparing a large-scale array of two-dimensional noble metal micro-nano patterns according to claim 1, wherein the selective dissolution is selective dissolution of PEO-b-P2VP crystal array patternThe number of times of dissolution is 1 to 2 times.
5. The method for preparing the two-dimensional noble metal micro-nano pattern large-scale array according to claim 1, wherein the process of the complex reaction of the gold ions and the P2VP is as follows: the completely washed sample was immersed in a 1.0% chloroauric acid/n-octanol solution and stored away from light 24h to ensure sufficient gold ion loading, and then the sample was repeatedly washed with n-octanol pure solvent to wash away the non-loaded gold particles deposited on the silicon wafer surface.
6. The method for preparing a two-dimensional noble metal micro-nano pattern large-scale array according to claim 1, wherein a sample carrying gold ions is cleaned by a plasma cleaning machine, wherein the cleaning parameters are as follows: the gas is air, the flow rate is 20sccm, the power is 80w, and the time is 5min.
CN202110655144.0A 2021-06-02 2021-06-11 Method for preparing two-dimensional noble metal micro-nano pattern large-scale array Active CN113461999B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110616345 2021-06-02
CN202110616345X 2021-06-02

Publications (2)

Publication Number Publication Date
CN113461999A CN113461999A (en) 2021-10-01
CN113461999B true CN113461999B (en) 2022-11-01

Family

ID=77870027

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110655144.0A Active CN113461999B (en) 2021-06-02 2021-06-11 Method for preparing two-dimensional noble metal micro-nano pattern large-scale array

Country Status (1)

Country Link
CN (1) CN113461999B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340693B (en) * 2022-08-15 2023-12-08 淮北师范大学 Preparation method of controllable patterning PDMS template

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011068960A2 (en) * 2009-12-02 2011-06-09 Northwestern University Block copolymer-assisted nanolithography
CN105355543B (en) * 2015-09-29 2017-12-22 淮北师范大学 Patterned semiconductor polymer thin membrane preparation method based on silk fiber
CN106495088A (en) * 2016-09-22 2017-03-15 北京科技大学 A kind of method of template hot pressing for wiener body structure surface pattern
CN110041547B (en) * 2019-04-18 2022-03-08 郑州大学 Method for constructing micro-nano pattern in polymer film lamella by utilizing selective dissolution
CN110116217B (en) * 2019-05-28 2022-03-11 郑州大学 Method for constructing two-dimensional gold nanoparticle pattern

Also Published As

Publication number Publication date
CN113461999A (en) 2021-10-01

Similar Documents

Publication Publication Date Title
CN113461999B (en) Method for preparing two-dimensional noble metal micro-nano pattern large-scale array
KR101494672B1 (en) Heat transfer medium and heat transfer method using the same
WO2013104141A1 (en) Method for using carbon source having multiple benzene rings to grow graphene over large area by chemical vapor deposition at low temperature
CN106588671A (en) Preparation of methylamine lead-iodine nanowire under air environment and application of photoelectric detector
Xue et al. Macromonomer crosslinking polymerized scaffolds for mechanically robust and flexible perovskite solar cells
US20100006820A1 (en) Silica nanowire comprising silicon nanodots and method of preparing the same
CN110983424B (en) Method for preparing large-area crack-free thick film photonic crystal on porous substrate
CN108821326B (en) ZnO nano material and preparation method thereof
CN110055589B (en) Large-size single-layer hexagonal boron nitride single crystal or film and preparation method thereof
CN108933193B (en) Transfer method and application of ferromagnetic semiconductor film
CN107240544B (en) A kind of preparation method of graphical film, thin film transistor (TFT) and memristor
Soleimanzadeh et al. Sequential microwave-assisted ultra-fast ZnO nanorod growth on optimized sol–gel seedlayers
CN112679764A (en) Au/Ni-BHT heterojunction conductive MOFs thin film material and controllable preparation method thereof
CN113089088A (en) Preparation method of two-dimensional transition metal chalcogenide
CN104851978A (en) Preparation method for micromolecule organic semiconductor single crystals
CN110993791A (en) Method for regulating and controlling growth of conductive polymer film crystal
KR20100037717A (en) Micropatterning method of thin p3ht films via plasma enhanced polymer transfer printing and manufacturing method of otfts having the p3ht micropatterned thin film as an active layer
KR20100092091A (en) Method of fabricting a nano-structure
KR100991861B1 (en) A fabrication method for nanodots using selective epitaxial growth and block copolymer nanotemplate and a semiconductor element manufactured thereby
CN113744929B (en) Preparation method of silver nanowire flexible conductive transparent film
CN108976684A (en) A kind of nanoporous polymer foams and preparation method thereof
CN110116217B (en) Method for constructing two-dimensional gold nanoparticle pattern
CN107344730A (en) A kind of preparation method of zinc-oxide nano column array
CN112538180A (en) Water-assisted polyethylene oxide single crystal film and preparation method thereof
CN114524956B (en) Method for producing oriented and stretchable organic semiconductor film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant