CN102500364A - Method for preparing nanometer Pt catalyst particles on Si substrate - Google Patents
Method for preparing nanometer Pt catalyst particles on Si substrate Download PDFInfo
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- CN102500364A CN102500364A CN2011103894271A CN201110389427A CN102500364A CN 102500364 A CN102500364 A CN 102500364A CN 2011103894271 A CN2011103894271 A CN 2011103894271A CN 201110389427 A CN201110389427 A CN 201110389427A CN 102500364 A CN102500364 A CN 102500364A
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Abstract
The invention discloses a method for preparing nanometer Pt catalyst particles on a Si substrate. The method for preparing the nanometer Pt catalyst particles on the Si substrate comprises the following steps of: cleaning the Si substrate, sputtering a Pt film on the cleaned Si substrate with a sputtering instrument, putting the Si substrate on which the Pt film is sputtered in the middle position of a quartz boat, putting the quartz boat into a constant-temperature area of a high-temperature tubular atmosphere furnace, importing N2 in a flow rate of 300 sccm for 20 minutes for removing air from the tubular furnace, stopping importing the N2, heating the tubular furnace, starting to import 100 sccm NH3 when the tubular furnace is heated to 900-1100 DEG C, keeping the constant temperature for 5-15 minutes and stopping importing the NH3; and finally, importing the N2 for 5 minutes for removing the NH3 from the tubular furnace and naturally cooling to normal temperature at the same time, to finish the preparation of the nanometer Pt catalyst particles on the Si substrate. According to the invention, the disadvantages of complex process and uneven particle size and distribution in the traditional method for preparing the nanometer Pt catalyst particles on the Si substrate are overcome.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related on the Si substrate, prepare nanometer Pt catalyst granules with high temperature ammonia etching method.
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; But when preparing monodimension nanometer material or height-oriented nano-array with the nanometer Pt catalyst granules that existing method is prepared; For example nano wire and array thereof or nanometer rods and array thereof; Before the preparation on the substrate self-assembled growth of catalyst granules such as nanometer Ni, Au, Pt and dispersion thereof inadequately evenly, the size and the density of particle is even inadequately, thereby the controlled preparation of monodimension nanometer material is produced harmful effect.
Summary of the invention
The purpose of this invention is to provide a kind of method that on the Si substrate, prepares nanometer Pt catalyst granules, prepare complex process, granular size and the shortcoming pockety that exists in the method for nanometer Pt catalyst granules on the existing Si substrate of solution.
The technical scheme that the present invention adopted is, a kind of method that on the Si substrate, prepares nanometer Pt catalyst granules is carried out according to following steps:
Step 1: preparation Pt 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, the Si substrate is placed on deionized water silicon chip to be cleaned up after soaking for 15 seconds in the hydrofluoric acid solution 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, with JFC-1600 type sputter sputter Pt film on the Si substrate that cleaned, the vacuum of the vacuum chamber during sputter in the sputter is 6.62 * 10
-3Pa, sputtering current are 40mA, and sputtering time is 30-360s;
Step 2: the preparation of nanometer Pt catalyst granules:
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace then together with quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, stops to feed N again
2, tube furnace begins to heat up, and when temperature reached 900-1100 ℃, feeding flow was the NH of 100sccm
3And keep closing NH behind the constant temperature 5-15min
3, 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 Si substrate preparation nanometer Pt.
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 invention has the beneficial effects as follows, can prepare on the Si substrate with high temperature ammonia etching method and be evenly distributed that the nanometer Pt catalyst granules of different sizes and density provides the catalyst granules of high-quality for the preparation of monodimension nanometer material.
Description of drawings
Fig. 1 is the XRD figure spectrum of the nanometer Pt catalyst granules that on the Si substrate, prepares of the inventive method;
Fig. 2 is that sputtering time is the SEM image of 30s in the nanometer Pt catalyst granules process that on the Si substrate, prepares of the inventive method;
Fig. 3 is that sputtering time is the SEM image of 120s in the nanometer Pt catalyst granules process that on the Si substrate, prepares of the inventive method;
Fig. 4 is that sputtering time is the SEM image of 240s in the nanometer Pt catalyst granules process that on the Si substrate, prepares of the inventive method;
Fig. 5 is that sputtering time is the SEM image of 360s in the nanometer Pt catalyst granules process 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 Pt catalyst granules, utilizes high temperature ammonia etching method on the Si substrate, to prepare nanometer Pt catalyst granules, specifically implements according to following steps:
Step 1: preparation Pt film on the Si substrate:
In this technology, we discover that the principal element that influences the Pt film thickness is a sputtering time, also are one of principal elements that influences Pt nano particle size and density.
At first, clean Si (111) substrate with the method for conventional cleaning Si sheet.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 being placed on volumetric concentration is with deionized water silicon chip to be cleaned up after soaking for 15 seconds in 10% the hydrofluoric acid solution; 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, with JFC-1600 type sputter sputter Pt film on the Si that cleaned (111) substrate.The vacuum of vacuum chamber is 6.62 * 10 during sputter
-3Pa, sputtering current are 40mA, and sputtering time is 30-360s.
Step 2: the preparation of nanometer Pt catalyst granules:
In this technology, we discover the principal element that influences Pt nano particle pattern:
1. etching temperature is to the influence of pattern;
2. etch period is to the influence of pattern.
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace then together with quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, closes N again
2, tube furnace begins to heat up, and when temperature reaches 900-1100 ℃ respectively, begins to feed the NH of 100sccm
3And keep respectively closing NH behind the constant temperature 5-15min
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 Si substrate preparation nanometer Pt.
Embodiment 1
Step 1: preparation Pt film on the Si substrate:
Sputtering time is to the influence of nanometer Pt catalyst particle size and density:
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, the Si substrate is placed on deionized water silicon chip to be cleaned up after soaking for 15 seconds in the hydrofluoric acid solution 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, uses deionized water rinsing after the taking-up.
Then, with JFC-1600 type sputter sputter Pt film on the Si that cleaned (111) substrate.The vacuum of vacuum chamber is 6.62 * 10 during sputter
-3Pa, sputtering current are 40mA, and sputtering time is 30s;
Step 2: the preparation of nanometer Pt catalyst granules:
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into quartz boat the flat-temperature zone of high-temperature tubular atmosphere furnace then, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, closes N again
2, tube furnace begins to heat up, and when temperature reaches 1000 ℃, begins to feed the NH of 100sccm
3And keep closing NH behind the constant temperature 10min
3, 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 Si substrate preparation nanometer Pt.
Embodiment 2
Step 1: preparation Pt 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, the Si substrate is placed on deionized water silicon chip to be cleaned up after soaking for 15 seconds in the hydrofluoric acid solution 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 uses deionized water rinsing, then, with JFC-1600 type sputter sputter Pt film on the Si that cleaned (111) substrate.The vacuum of vacuum chamber is 6.62 * 10 during sputter
-3Pa, sputtering current are 40mA, and sputtering time is 120s.
Step 2: the preparation of nanometer Pt catalyst granules:
The ammonia etching temperature is definite in tube furnace:
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into quartz boat the flat-temperature zone of high-temperature tubular atmosphere furnace then, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, closes N again
2, tube furnace begins to heat up, and when temperature reaches 900 ℃, 1000 ℃, 1100 ℃ respectively, begins to feed the NH of 100sccm
3And keep closing NH behind the constant temperature 15min at 900 ℃ respectively
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 Si substrate preparation nanometer Pt.
Embodiment 3
Preparation Pt 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, the Si substrate is placed on deionized water silicon chip to be cleaned up after soaking for 15 seconds in the hydrofluoric acid solution 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, with JFC-1600 type sputter sputter Pt film on the Si substrate that cleaned, the vacuum of the vacuum chamber during sputter in the sputter is 6.62 * 10
-3Pa, sputtering current are 40mA, and sputtering time is 360s;
Step 2: the preparation of nanometer Pt catalyst granules:
The ammonia etch period is definite in tube furnace:
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into quartz boat the flat-temperature zone of high-temperature tubular atmosphere furnace then, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, closes N again
2, tube furnace begins to heat up, and when temperature reaches 1100 ℃, begins to feed the NH of 100sccm
3And keep closing NH behind the constant temperature 5min
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 Si substrate preparation nanometer Pt.
The Pt catalyst granules that makes among the above embodiment is carried out SEM characterize, find that through morphology analysis the nanometer Pt catalyst granules that obtains is evenly distributed, size reduces with sputtering time and reduces, and density reduces with sputtering time and increases.
The Pt catalyst granules of three embodiment obtaining is carried out SEM characterize, find, the nanometer Pt catalyst particle size that the ammonia etching temperature obtains when being 1000 ℃, be evenly distributed through morphology analysis.So, be the best when the ammonia etching temperature is set at 1000 ℃ in tube furnace.
The Pt catalyst granules of three embodiment obtaining is carried out SEM characterize, find, the nanometer Pt catalyst particle size that the ammonia etch period obtains during for 10min, be evenly distributed through morphology analysis.So, be the best when the ammonia etch period is set at 10min in tube furnace.
The inventive method is utilized high temperature ammonia lithographic method on Si (111) substrate, to have prepared and is evenly distributed, the nanometer Pt catalyst granules of different size and density.
Fig. 1 is the XRD figure spectrum (the XRD figure spectrum of each sample of our preparation is the same) of the nanometer Pt catalyst granules that on the Si substrate, prepares of the present invention; As can be seen from the figure; Three diffraction maximums (111); (200) and the diffraction maximum of (220) and ASTM data Pt meet finely, XRD figure spectrum result shows that prepared sample is the Pt particle.
Fig. 2-Fig. 5 is that sputtering time is respectively the SEM image of 30s, 120s, 240s, 360s in the nanometer Pt catalyst granules process that on the Si substrate, prepares of method of the present invention.From figure, can observe each sample a large amount of distributions and nanometer Pt catalyst granules of uniform size are arranged, nanometer Pt catalyst particle size reduces with sputtering time and reduces in four samples, and density reduces with sputtering time and increases.Thereby even particle distribution, size and controllable density system.
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 Pt catalyst granules with high temperature ammonia etching method on the Si substrate, and data by MoM and MEI, and the method is simple, granular size and being evenly distributed.
Claims (3)
1. a method that on the Si substrate, prepares nanometer Pt catalyst granules is characterized in that, carries out according to following steps:
Step 1: preparation Pt 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, the Si substrate is placed on deionized water silicon chip to be cleaned up after soaking for 15 seconds in the hydrofluoric acid solution 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, takes out the back and uses deionized water rinsing, then; Sputter Pt film on the Si substrate that cleaned, during sputter in the sputter vacuum of vacuum chamber be 6.62 * 10
-3Pa, sputtering current are 40mA, and sputtering time is 30-360s;
Step 2: the preparation of nanometer Pt catalyst granules:
The Si sheet of crossing the Pt film to sputter in the step 2 is put into the centre position of quartz boat, puts into the flat-temperature zone of high-temperature tubular atmosphere furnace then together with quartz boat, and feeding flow is the N of 300sccm
220min in order to remove the air in the tube furnace, stops to feed N again
2, tube furnace begins to heat up, and when temperature reached 900-1100 ℃, feeding flow was the NH of 100sccm
3And keep closing NH behind the constant temperature 5-15min
3, 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 Si substrate preparation nanometer Pt.
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%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103128303A (en) * | 2013-02-28 | 2013-06-05 | 北京科技大学 | Method for preparing nanogold by vapor deposition process |
| CN108031832A (en) * | 2017-12-06 | 2018-05-15 | 青岛大学 | A kind of platinum metal alloy nano particle with loose structure and preparation method thereof |
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| WO2000073205A1 (en) * | 1999-06-02 | 2000-12-07 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes and catalysts therefor |
| CN1699151A (en) * | 2004-05-21 | 2005-11-23 | 龚平 | Process for preparing nano carbon tube |
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- 2011-11-30 CN CN2011103894271A patent/CN102500364A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073205A1 (en) * | 1999-06-02 | 2000-12-07 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes and catalysts therefor |
| CN1699151A (en) * | 2004-05-21 | 2005-11-23 | 龚平 | Process for preparing nano carbon tube |
Non-Patent Citations (3)
| Title |
|---|
| 《 Diamond and Related Materials》 20031231 Jae-Hee Han，et al. "Growth characteristics of carbon nanotubes using platinum catalyst by plasma enhanced chemical vapor deposition , * |
| JAE-HEE HAN，ET AL.: ""Growth characteristics of carbon nanotubes using platinum catalyst by plasma enhanced chemical vapor deposition", 《 DIAMOND AND RELATED MATERIALS》 * |
| 李刚，等: "高温氨预处理对单晶硅衬底上镍薄膜显微结构的影响", 《材料热处理学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103128303A (en) * | 2013-02-28 | 2013-06-05 | 北京科技大学 | Method for preparing nanogold by vapor deposition process |
| CN108031832A (en) * | 2017-12-06 | 2018-05-15 | 青岛大学 | A kind of platinum metal alloy nano particle with loose structure and preparation method thereof |
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Application publication date: 20120620 |