CN102500380A - Method for preparing nanometer Ni catalyst particles on Si substrate - Google Patents
Method for preparing nanometer Ni catalyst particles on Si substrate Download PDFInfo
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- CN102500380A CN102500380A CN2011103893029A CN201110389302A CN102500380A CN 102500380 A CN102500380 A CN 102500380A CN 2011103893029 A CN2011103893029 A CN 2011103893029A CN 201110389302 A CN201110389302 A CN 201110389302A CN 102500380 A CN102500380 A CN 102500380A
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Abstract
The invention discloses a method for preparing nanometer Ni catalyst particles on an Si substrate. The method comprises the following steps: cleaning the Si substrate, placing the cleaned Si substrate in an ethanol solution of nickel nitrate to perform ultrasonic vibration, placing the obtained substrate in a muffle furnace to dry and obtain an Si substrate coated with an Ni film, placing the prepared Si substrate coated with the Ni film in a quartz boat, placing the quartz boat in a high-temperature tubular atmosphere furnace, injecting N2 to remove air in the tubular furnace, heating, adopting the high temperature ammonia etching method to prepare nanometer Ni catalyst particles on the Si substrate, finally injecting N2 to remove NH3 in the tubular furnace, and naturally cooling to the room temperature so as to prepare the nanometer Ni catalyst particles on the Si substrate. By adopting the method disclosed by the invention, the defects of the existing method for preparing nanometer Ni catalyst particles on the Si substrate, that the technology is complex and the size and distribution of the particles are nonuniform can be overcome.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of method that on the Si substrate, prepares nanometer Ni catalyst granules.
Background technology
Since the discovery of the CNT nineties in last century, monodimension nanometer material has become one of focus of people's researchs.See that from the angle of basic science character such as the power of nano material, heat, electricity, light, magnetic have very big-difference with the conventional blocks material, its research has abundant scientific contents and important scientific value.See from the angle of technical application; Advancing by leaps and bounds of electronic information technology; Microminiaturization, sensitivity, integrated level to device are had higher requirement; The basic composition element characteristic size of device has arrived nanometer scale, has reached the limit of traditional material and preparation of devices, processing, structure, must have the new science and technology based on the nano material system just can address this problem.Monodimension nanometer material is the new foothold of 21st century scientific research, is expected to become the key composition of following nano-device, and its controllable growth is one of crucial matter of science and technology of its device.
At present; Transition-metal catalyst is widely used in the preparation of monodimension nanometer material; In order to prepare monodimension nanometer material or height-oriented nano-array; For example nano wire and array thereof or nanometer rods and array thereof, before the preparation monodimension nanometer material on the substrate size and the uniformity coefficient of the self-assembled growth of catalyst granules such as nanometer Ni, Au, Pt and dispersed uniform degree thereof, particle very important to the controlled preparation of monodimension nanometer material.And existing method prepares the method for nanometer Ni catalyst granules and has complex process, and shortcomings such as granular size and skewness influence the preparation of monodimension nanometer material or height-oriented nano-array.
Summary of the invention
The purpose of this invention is to provide a kind of method that on the Si substrate, prepares nanometer Ni catalyst granules, prepare complex process, granular size and the shortcoming pockety that exists in the method for nanometer Ni catalyst granules on the existing Si substrate of solution.
The technical scheme that the present invention adopted is that a kind of method that on the Si substrate, prepares nanometer Ni catalyst granules is characterized in that, carries out according to following steps:
Step 1: preparation Ni film on the Si substrate:
At first; It is that 1: 1 the red fuming nitric acid (RFNA) and the mixed solution of hydrogen peroxide solution boil 10min that the Si substrate is put into volume ratio; Putting into is that 1: 1: 6 the mixed solution of hydrogen peroxide solution, ammoniacal liquor and deionized water boils 10min by volume again, after soaking for 15 seconds in the Si substrate hydrofluoric acid solution, with deionized water silicon chip is cleaned up again; At last; It is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that silicon chip is placed on volume ratio; Take out the back and use deionized water rinsing, then, the ethanolic solution sonic oscillation of the Si substrate that cleaned being put into the nickel nitrate that configures took out after 2 hours; Put into the Muffle furnace drying afterwards, obtain being coated with the Si substrate of Ni film;
Step 2: the preparation of nanometer Ni catalyst granules:
The Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace together with quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature in the stove afterwards, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 750 ℃～850 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind constant temperature 20～40min
3, last, feed N
25min is to remove the NH in the tube furnace
3, naturally cool to normal temperature simultaneously, promptly accomplish catalyst granules at the nanometer Ni of Si substrate preparation.
Characteristics of the present invention also are,
Si substrate described in the step 1 is Si (a 111) substrate.
The volumetric concentration of the hydrofluoric acid solution described in the step 1 is 10%.
The mass concentration of the ethanolic solution of the nickel nitrate described in the step 1 is 2%.
The invention has the beneficial effects as follows that through the nanometer Ni catalyst granules that on the Si substrate, prepares with high temperature ammonia etching method, the nanometer Ni catalysed particulate that obtains size, be evenly distributed, density is big, and the catalyst granules of high-quality is provided for the preparation of monodimension nanometer material.
Description of drawings
Fig. 1 is the XRD figure spectrum of the nanometer Ni catalyst granules that on the Si substrate, prepares of the inventive method;
Fig. 2 is the SEM image of the nanometer Ni catalyst granules that on the Si substrate, prepares of the inventive method.
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is elaborated.
The present invention provides a kind of method that on the Si substrate, prepares nanometer Ni catalyst granules, utilizes high temperature ammonia etching method on the Si substrate, to prepare nanometer Ni catalyst granules, specifically implements according to following steps:
Step 1: preparation Ni film on the Si substrate:
At first, Si (111) substrate is put into the red fuming nitric acid (RFNA) of 1: 1 volume ratio and the mixed solution of hydrogen peroxide solution boils 10min; The mixed solution of putting into again by hydrogen peroxide solution, ammoniacal liquor and the deionized water of 1: 1: 6 volume ratio boils 10min; Again silicon chip is placed in 10% hydrofluoric acid solution and with deionized water silicon chip is cleaned up after soaking for 15 seconds; At last, it is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that silicon chip is placed on volume ratio, uses deionized water rinsing after the taking-up.
Then, configuration quality concentration is 2% nickel nitrate ethanolic solution, the Si substrate that cleaned is put into the nickel nitrate ethanolic solution sonic oscillation that configures take out after 2 hours, puts into the Muffle furnace drying, obtains being coated with the Si substrate of Ni film;
Step 2: the preparation of nanometer Ni catalyst granules:
The Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace to quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature again, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 750 ℃～850 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind constant temperature 20～40min
3At last, feed 5min N
2To remove the NH in the tube furnace
3, normal temperature is reduced in cooling naturally simultaneously, promptly accomplishes the catalyst granules at the nanometer Ni of Si substrate preparation.
Embodiment 1
Step 1: at first, Si (111) substrate is put into the red fuming nitric acid (RFNA) of 1: 1 volume ratio and the mixed solution of hydrogen peroxide solution boils 10min; The mixed solution of putting into again by hydrogen peroxide solution, ammoniacal liquor and the deionized water of 1: 1: 6 volume ratio boils 10min; Again Si (111) substrate is placed in 10% hydrofluoric acid solution and with deionized water silicon chip is cleaned up after soaking for 15 seconds; At last, it is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that Si (111) substrate is placed on volume ratio, uses deionized water rinsing after the taking-up.Then, configuration quality concentration is 2% nickel nitrate ethanolic solution, the Si that cleaned (111) substrate is put into the nickel nitrate ethanolic solution sonic oscillation that configures take out after 2 hours, puts into the Muffle furnace drying, obtains being coated with the Si substrate of Ni film.
Step 2: the Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace to quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature again, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 750 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind the constant temperature 30min
3At last, feed 5min N
2To remove the NH in the tube furnace
3, normal temperature is reduced in cooling naturally simultaneously, promptly accomplishes the catalyst granules at the nanometer Ni of Si substrate preparation.
Embodiment 2
Step 1: at first, Si (111) substrate is put into the red fuming nitric acid (RFNA) of 1: 1 volume ratio and the mixed solution of hydrogen peroxide solution boils 10min; The mixed solution of putting into again by hydrogen peroxide solution, ammoniacal liquor and the deionized water of 1: 1: 6 volume ratio boils 10min; Again Si (111) substrate is placed in 10% hydrofluoric acid solution and with deionized water Si (111) substrate is cleaned up after soaking for 15 seconds; At last, it is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that Si (111) substrate is placed on volume ratio, uses deionized water rinsing after the taking-up.
Then, configuration quality concentration is 2% nickel nitrate ethanolic solution, the Si substrate that cleaned is put into the nickel nitrate ethanolic solution sonic oscillation that configures take out after 2 hours, puts into the Muffle furnace drying, obtains being coated with the Si substrate of Ni film.
Step 2: the Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace to quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature again, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 800 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind the constant temperature 20min
3At last, feed 5min N
2To remove the NH in the tube furnace
3, normal temperature is reduced in cooling naturally simultaneously, promptly accomplishes the catalyst granules at the nanometer Ni of Si substrate preparation.
Embodiment 3
Step 1: at first, Si (111) substrate is put into the red fuming nitric acid (RFNA) of 1: 1 volume ratio and the mixed solution of hydrogen peroxide solution boils 10min; The mixed solution of putting into again by hydrogen peroxide solution, ammoniacal liquor and the deionized water of 1: 1: 6 volume ratio boils 10min; Again Si (111) substrate is placed in 10% hydrofluoric acid solution and with deionized water Si (111) substrate is cleaned up after soaking for 15 seconds; At last, it is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that Si (111) substrate is placed on volume ratio, uses deionized water rinsing after the taking-up.Then, configuration quality concentration is 2% nickel nitrate ethanolic solution, the Si substrate that cleaned is put into the nickel nitrate ethanolic solution sonic oscillation that configures take out after 2 hours, puts into the Muffle furnace drying, obtains being coated with the Si substrate of Ni film.
Step 2: the Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace to quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature again, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 850 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind the constant temperature 40min
3At last, feed 5min N
2To remove the NH in the tube furnace
3, normal temperature is reduced in cooling naturally simultaneously, promptly accomplishes the catalyst granules at the nanometer Ni of Si substrate preparation.
In the research process of the method for carrying out this invention, we find that the principal element that influences nanometer Ni catalyst granules pattern has:
1) etching temperature is to the influence of pattern;
2) etch period is to the influence of pattern.
Characterize so three kinds of nanometer Ni catalyst granules that above embodiment is obtained carry out SEM, find through morphology analysis, the nanometer Ni catalysed particulate size that etching temperature obtains when being 800 ℃, be evenly distributed, density is big.So, be preferred version when the ammonia etching temperature is set at 800 ℃ in tube furnace.
And three kinds of nanometer Ni catalyst granules that obtain are carried out SEM characterize, find through morphology analysis, the Ni nano particle size that etch period obtains during for 30min, be evenly distributed, density is big.So, be preferred version when the ammonia etch period is set at 30min in tube furnace.
The inventive method utilizes high temperature ammonia lithographic method on Si (111) substrate, to prepare the nanometer Ni catalyst granules that distributes with size is even, density is bigger.As shown in Figure 1, be the XRD figure spectrum of the nanometer Ni catalyst granules that on the Si substrate, prepares of the present invention, as can be seen from the figure, the diffraction maximum of all diffraction maximums and ASTM data Ni meets fine, and XRD figure is composed the result and is shown that prepared sample is the Ni particle.
Fig. 2 is the SEM image of the nanometer Ni catalyst granules that on the Si substrate, prepares of the present invention; It is the sign of the nanometer Ni catalyst granules that on the Si substrate, prepares under the preferred version; From figure, can observe and generate a large amount of distributions and nanometer Ni catalyst granules of uniform size, diameter is 100～150nm.
The one dimension semiconductor nano material is expected to become the key composition of following nano-device; Be the important member of semiconductor nano material; In future very big application prospect being arranged, is the material foundation that use in photoelectronics such as following semiconductor laser and photodetector, optical storage of data, high-performance ultraviolet detector and high temperature, high frequency, large power semiconductor device and microelectronics field.Therefore, the controlled Study on Preparation Technology of one dimension semiconductor nano material is occupied very consequence in the research of present whole monodimension nanometer material.In the technology of preparation monodimension nanometer material, the big or small uniformity coefficient of nanometer Ni, Pt catalyst granules dispersed uniform degree, particle is very important to the preparation of monodimension nanometer material on the substrate.Among the present invention, we prepare nanometer Ni catalyst granules with high temperature ammonia etching method on the Si substrate, and the method is simple, granular size and being evenly distributed.
Claims (4)
1. a method that on the Si substrate, prepares nanometer Ni catalyst granules is characterized in that, carries out according to following steps:
Step 1: preparation Ni film on the Si substrate:
At first; It is that 1: 1 the red fuming nitric acid (RFNA) and the mixed solution of hydrogen peroxide solution boil 10min that the Si substrate is put into volume ratio; Putting into is that 1: 1: 6 the mixed solution of hydrogen peroxide solution, ammoniacal liquor and deionized water boils 10min by volume again, after soaking for 15 seconds in the Si substrate hydrofluoric acid solution, with deionized water silicon chip is cleaned up again; At last; It is to boil 15min in 1: 1: 6 the mixed solution of hydrogen peroxide solution, hydrochloric acid and deionized water that silicon chip is placed on volume ratio; Take out the back and use deionized water rinsing, then, the ethanolic solution sonic oscillation of the Si substrate that cleaned being put into the nickel nitrate that configures took out after 2 hours; Put into the Muffle furnace drying afterwards, obtain being coated with the Si substrate of Ni film;
Step 2: the preparation of nanometer Ni catalyst granules:
The Si substrate that is coated with the Ni film that makes step 1 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace together with quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, rises to 310 ℃ with temperature in the stove afterwards, keeps closing N behind 310 ℃ of constant temperature 30min
2Then, continue to be warming up to 750 ℃～850 ℃, feed the NH that flow is 100sccm this moment
3, keep closing NH behind constant temperature 20～40min
3, last, feed N
25min is to remove the NH in the tube furnace
3, naturally cool to normal temperature simultaneously, promptly accomplish catalyst granules at the nanometer Ni of Si substrate preparation.
2. method according to claim 1 is characterized in that, the Si substrate described in the step 1 is Si (a 111) substrate.
3. method according to claim 1 is characterized in that, the volumetric concentration of the hydrofluoric acid solution described in the step 1 is 10%.
4. method according to claim 1 is characterized in that, the mass concentration of the ethanolic solution of the nickel nitrate described in the step 1 is 2%.
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| CN108609579A (en) * | 2018-04-25 | 2018-10-02 | 中原工学院 | A method of preparing patterned silicon substrate without photoetching technique |
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| CN101913552A (en) * | 2010-08-02 | 2010-12-15 | 清华大学 | Method for preparing suspension micro-sensitive structure based on aluminum sacrificial layer process |
Non-Patent Citations (4)
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| 《固体电子学研究与进展》 20090930 倪鹤南 等， "Ni纳米晶制备及其在MOS电容中存储特性研究" 第460-464页 第29卷, 第3期 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108609579A (en) * | 2018-04-25 | 2018-10-02 | 中原工学院 | A method of preparing patterned silicon substrate without photoetching technique |
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Application publication date: 20120620 |