CN117702086A - Electro-spray atomic layer vapor deposition film making device - Google Patents
Electro-spray atomic layer vapor deposition film making device Download PDFInfo
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- CN117702086A CN117702086A CN202311610980.2A CN202311610980A CN117702086A CN 117702086 A CN117702086 A CN 117702086A CN 202311610980 A CN202311610980 A CN 202311610980A CN 117702086 A CN117702086 A CN 117702086A
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- 238000007740 vapor deposition Methods 0.000 title claims abstract description 9
- 239000007921 spray Substances 0.000 title claims description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 86
- 230000008021 deposition Effects 0.000 claims abstract description 83
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 238000012216 screening Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims description 85
- 238000005485 electric heating Methods 0.000 claims description 22
- 230000005684 electric field Effects 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000010354 integration Effects 0.000 claims description 5
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- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 3
- 238000002385 metal-ion deposition Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 13
- 238000000766 differential mobility spectroscopy Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 22
- 238000000231 atomic layer deposition Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003877 atomic layer epitaxy Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000005274 electrospray deposition Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- 239000010409 thin film Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
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Abstract
The invention relates to an electrospray atomic layer vapor deposition film forming device, which comprises the following components in sequence from left to right: an electrospray electrode formed by an electrospray capillary with an outer sleeve, an electrode plate with a square through hole in the center, an ion screening area formed by a high-voltage electrode and a ground electrode which are oppositely arranged, an ion deflection/detection plate and a deposition plate which are oppositely arranged; a radiation heating source is arranged outside the gap between the electrode plate and the ion screening area and is used for heating the area between the electrode plate and the ion screening area; the deposition plate on the side of the ion screening area far from the electrode plate can reciprocate along the X-axis direction or rotate parallel to the rotating shaft of the Z-axis. The invention has the classifying and screening functions of high-field asymmetric waveform ion mobility spectrometry on ions with different sizes under normal pressure, and solves the problem that metal ions with different particle diameters are co-deposited and a single-performance metal film is difficult to obtain.
Description
Technical Field
The invention relates to an electrospray atomic layer vapor deposition film-making device, which utilizes electrospray to obtain metal cluster ions with different particle size distributions, and utilizes the pre-separation of a high-field asymmetric waveform ion mobility spectrometry to realize the selective passage of ions through a separation area; finally, on the basis of detecting the particle size distribution of the metal cluster ions, a metal film which is uniformly distributed in space is obtained on a deposition plate by using a moving platform.
Background
Atomic layer deposition (atomiclayer deposition, ALD), also known as atomic layer epitaxy (atomiclayer epitaxy, ALE), is a chemical vapor deposition technique based on an ordered, surface self-saturation reaction. Atomic layer deposition technology originated in the sixty of the last century and was first reported by soviet scientists aleskovski and Koltsov, and was subsequently developed and perfected by Suntalo doctor, finland, based on the demand for high quality ZnS: mn thin film materials for electroluminescent thin film flat panel displays. However, due to the complicated surface chemical process, the atomic layer deposition technology has not been developed greatly in the beginning, until nineties of the last century, and with the rise of the semiconductor industry, the requirements on various component sizes, integration levels and the like are higher and higher, so that the atomic layer deposition technology is in the gold stage of development. In the 21 st century, atomic layer deposition technology has received increasing attention both in basic research and in practical use as commercial ALD instruments have been developed to accommodate various manufacturing requirements.
Electrospray deposition refers to the process of electrochemical deposition of a metal or alloy from an aqueous, nonaqueous or molten salt of its compound. In electrospray deposition, a coating apparatus applies high pressure to a flowing liquid to convert it into microscopic particles, each of which evaporates when it reaches a target area, depositing a solid precipitate from the original solution.
Disclosure of Invention
The invention aims to solve the problem that single-performance metal films are difficult to obtain by codeposition of metal ions with different particle diameters by classifying and screening ions with different sizes under normal pressure through a high-field asymmetric waveform ion mobility spectrometry.
To achieve the purpose, the invention adopts the following technical scheme:
an electrospray atomic layer vapor deposition film forming device takes the left-to-right direction as the X-axis direction, the top-to-bottom direction as the Y-axis direction and the directions perpendicular to the X-axis and the Y-axis as the Z-axis direction;
the device comprises the following components from left to right: an electrospray electrode (1) formed by an electrospray capillary tube with an outer sleeve, an electrode plate (2) with a square through hole (3) at the center, an ion screening area (12) formed by a high-voltage electrode (5) and a ground electrode (7) which are oppositely arranged, an ion deflection/detection plate (8) and a deposition plate (9) which are oppositely arranged;
a radiation heating source (4) is arranged outside the gap between the electrode plate (2) and the ion screening area and is used for heating the area between the electrode plate (2) and the ion screening area; the deposition plate (9) positioned on one side of the ion screening area (12) far away from the electrode plate (2) can reciprocate along the X-axis direction or rotate parallel to the rotating shaft of the Z-axis.
The electrospray capillary needle is sleeved in the outer sleeve; the outlet of the electrospray electrode (1) faces the square through hole (3);
the high-voltage electrode (5) is connected with the high-voltage power supply (6); the ground electrode (7) is grounded;
positive high voltage is applied to an electrospray capillary needle of the electrospray electrode (1), the electrode plate (2) is grounded, and spray is formed in a region between the positive high voltage and the electrode plate; the metal precursor solution flows through the electrospray capillary, the carrier gas flows through the area between the inner wall surface of the outer sleeve and the outer wall surface of the electrospray capillary, and under the driving of the carrier gas, the metal ion clusters pass through the square through holes (3) to move towards the ion screening area (12);
the lower surface of the flat high-voltage electrode (5) and the upper surface of the flat ground electrode (7) below the flat high-voltage electrode are oppositely arranged, and an ion screening area (12) is formed between the flat high-voltage electrode and the flat ground electrode along the X-axis direction.
The deposition plate (9) is a flat plate, the upper surface of the deposition plate is parallel to the X axis, and the upper surface of the flat plate is parallel to the upper surface of the ground electrode (7), or the upper surface of the deposition plate is positioned below the plane of the upper surface of the ground electrode (7); a heating plate (10) for heating the deposition plate (9) is arranged at the lower part of the deposition plate (9), and the heating plate (10) is fixed on a movable platform (14) capable of reciprocating along the X-axis direction; an electric heating element (13) (such as one or more of an electric heating wire, an electric heating rod and an electric heating block) is arranged in the heating plate (10)
Or the deposition plate (9) is a columnar or cylindrical (such as a cylinder) axisymmetric body, the axis of the axisymmetric body is parallel to the Z axis, and the top of the columnar axisymmetric body is positioned on the plane or below the plane of the upper surface of the ground electrode (7); an electric heating element (13) (such as one or more of an electric heating wire, an electric heating rod and an electric heating block) for heating the deposition plate (9) is arranged inside the deposition plate (9); a rotating shaft is arranged in the columnar axisymmetric body along the axis of the columnar axisymmetric body in a penetrating way, one end of the rotating shaft is fixedly connected with or in transmission connection with an output shaft of a motor, and the columnar axisymmetric body is driven to rotate along the axis of the columnar axisymmetric body through the motor through the rotating shaft;
when the deposition plate (9) is a flat plate, the lower part of the moving platform (14) is provided with rollers, so that the moving platform (14) can reciprocate along the X-axis direction; a temperature probe (11) or a temperature sensor is arranged in the heating plate (10);
or when the deposition plate (9) is a columnar axisymmetric body, one end of the rotating shaft is in transmission connection with an output shaft of a motor through a chain or a belt; a temperature probe (11) or a temperature sensor is arranged inside the deposition plate (9);
the temperature probe (11) or the temperature sensor is connected with the temperature controller; the electric heating element (13) is connected with an external power supply through a temperature controller.
The lower surface of the flat ion deflection/detection plate (8) is parallel to the X axis, and the lower surface of the flat ion deflection/detection plate is parallel to the lower surface of the high-voltage electrode (5) or the lower surface of the flat ion deflection/detection plate is positioned above the plane where the lower surface of the high-voltage electrode (5) is positioned;
the ion deflection/detection plate (8) is made of metal or an insulating sheet with a metal coating on the side facing the deposition plate (9), and the substrate is connected with a current detector.
Introducing liquid metal precursor solution into the electrospray capillary needle;
when the deposition plate (9) is a flat plate, the deposition plate (9) and the heating plate (10) move at a uniform speed along the X axis under the action of the moving platform (14) in the deposition process, so that a uniformly distributed metal film is obtained on the upper surface of the deposition plate (9); the thickness of the deposited film is realized by regulating and controlling the moving speed of the moving platform (14);
or when the deposition plate (9) is a columnar axisymmetric body, the deposition plate (9) rotates at a constant speed under the action of a motor in the deposition process, so that a uniformly distributed metal film is obtained on the surface of the deposition plate (9); the thickness of the deposited film is achieved by the rotational speed of the motor output.
When the deposition plate (9) is a flat plate, at least one of the deposition plate (9) and the heating plate (10) is made of conductive material (such as metal) as an electrode plate A; or when the deposition plate (9) is a columnar axisymmetric body, the deposition plate (9) is made of conductive material (such as metal) and is used as an electrode plate A;
applying an electric field between the ion deflection/detection plate (8) and the electrode plate A to detect metal ions firstly, and then separating and depositing: when metal ions are detected, the electric field direction is pointed to the ion deflection/detection plate (8) by the deposition plate (9); during metal ion deposition, the electric field direction is directed from the ion deflection/detection plate (8) to the deposition plate (9).
Applying a high-field asymmetric waveform voltage and a direct current compensation voltage to the high-voltage electrode (5), wherein the frequency of the high-field asymmetric waveform radio frequency voltage is 0.1MHz to 100MHz, and the integration area of the high-field asymmetric waveform radio frequency voltage and the low-field voltage in one period is equal to time: the high field voltage is a fixed value in the range of 1000V to 10000V, and the low field voltage is a fixed value in the range of 100V to 500V; the DC compensation voltage is between-50V and 50V, and the scanning step length is less than or equal to 0.5V (for example, 0.1-0.5V);
when metal ions are detected, the high-field asymmetric waveform radio frequency voltage is fixed, and the direct current compensation voltage is scanned step by step, so that metal ions with different sizes pass through an ion screening area (12), the size distribution of the metal ions is obtained, and the direct current compensation voltage value corresponding to the peak signal intensity of the metal ion groups with multiple sizes is obtained; during deposition, the high-field asymmetric waveform radio frequency voltage is fixed, and meanwhile, the direct current compensation voltage is fixed at a direct current compensation voltage value corresponding to a metal ion group peak signal with a required size, so that the ion group with the size only passes through an ion screening area (12) to screen the ion group with the specific size.
The width of the square through hole (3) in the Z-axis direction is larger than or equal to the width of the corresponding high-voltage electrode (5) and the corresponding ground electrode (7);
and a direct-current high voltage is applied to the electrospray capillary (1), the voltage amplitude is 1kV to 10kV, and the electrode plate (2) is grounded.
The radiation heating source (4) can be one or more than two of an infrared heating lamp, an incandescent lamp, a halogen tungsten lamp and a halogen lamp; the heating temperature of the area between the electrode plate (2) and the ion screening area is between room temperature and 400 ℃, and the temperature is regulated by adjusting the power of the radiation heating source (4);
the heating temperature of the heating plate (9) ranges from room temperature to 300 ℃.
The invention has the following advantages:
the novel device and the method for preparing the metal film by atomic layer deposition, which are single in structure and uniform in distribution, are developed, the screening and selective deposition of metal cluster ions with different sizes under normal pressure are realized, and technical support is provided for researching the structure-activity relationship between the structure and the performance and preparing the high-performance film material.
Drawings
FIG. 1 is a schematic diagram of an electrospray atomic layer vapor deposition film forming device.
Electrospray electrode (1), electrode plate (2), square through hole (3), radiation heating source (4), high-voltage electrode (5), high-voltage power supply (6), ground electrode (7), ion deflection/detection plate (8), deposition plate (9), heating plate (10), temperature probe (11), ion screening area (12), and electric heating element (13);
fig. 2. Intensity distribution of copper ions at different dc offset voltages.
FIG. 3A Cu atomic layer film prepared by ion screening (left panel) and non-screening (right panel) deposition on Al2O3 substrate respectively based on compensation voltage of 8.5V of the deposition film forming device.
Detailed Description
An electrospray atomic layer vapor deposition film forming device takes the left-to-right direction as the X-axis direction, the top-to-bottom direction as the Y-axis direction and the directions perpendicular to the X-axis and the Y-axis as the Z-axis direction;
the device comprises the following components from left to right: an electrospray electrode 1 formed by an electrospray capillary with an outer sleeve, an electrode plate 2 with a square through hole 3 at the center, an ion screening area 12 formed by a high-voltage electrode 5 and a ground electrode 7 which are oppositely arranged, an ion deflection/detection plate 8 and a deposition plate 9 which are oppositely arranged;
a radiation heating source 4 is arranged outside the gap between the electrode plate 2 and the ion screening area and is used for heating the area between the electrode plate 2 and the ion screening area; the deposition plate 9 on the side of the ion screening zone 12 remote from the electrode plate 2 is reciprocally movable in the X-axis direction.
The electrospray capillary needle is sleeved in the outer sleeve; the outlet of the electrospray electrode 1 faces the square through hole 3;
the high-voltage electrode 5 is connected with the high-voltage power supply 6; the ground electrode 7 is grounded;
positive high voltage is applied to an electrospray capillary needle of the electrospray electrode 1, the electrode plate 2 is grounded, and spray is formed in a region between the positive high voltage and the electrode plate; the metal precursor solution flows through the electrospray capillary, the carrier gas flows through the area between the inner wall surface of the outer sleeve and the outer wall surface of the electrospray capillary, and under the driving of the carrier gas, the metal ion clusters pass through the square through holes 3 to move towards the ion screening area 12;
the lower surface of the flat plate-like high-voltage electrode 5 and the upper surface of the flat plate-like ground electrode 7 located therebelow are disposed opposite to each other with an ion screening area 12 formed therebetween in the X-axis direction.
The deposition plate 9 is a flat plate, the upper surface of the deposition plate is parallel to the X axis, and the upper surface of the flat plate is parallel to the upper surface of the ground electrode 7; a heating plate 10 for heating the deposition plate 9 is arranged at the lower part of the deposition plate 9, and the heating plate 10 is fixed on a moving platform 14 capable of reciprocating along the X-axis direction; an electric heating wire heating element 13 is arranged in the heating plate 10;
when the deposition plate 9 is a flat plate, the movable platform 14 is a flat plate, 4 rolling rollers are fixedly arranged at the lower part of the movable platform through a bracket, the flat plate is pushed along the X-axis direction, and the movable platform 14 can reciprocate along the X-axis direction through the rotation of the rollers; a temperature probe 11 is arranged in the heating plate 10;
the temperature probe 11 is connected with a temperature controller; the electric heating wire and the electric heating element 13 are connected with an external power supply through a temperature controller.
The lower surface of the flat plate-shaped ion deflection/detection plate 8 is arranged parallel to the X axis, and the lower surface of the flat plate-shaped ion deflection/detection plate is parallel to the lower surface of the high-voltage electrode 5;
the ion deflection/detection plate 8 is a metal plate (copper plate) which is connected to a current detector.
Introducing liquid metal precursor solution into the electrospray capillary needle;
when the deposition plate 9 is a flat plate, the deposition plate 9 and the heating plate 10 move at a uniform speed along the X axis under the action of the moving platform 14 in the deposition process, so that a uniformly distributed metal film is obtained on the upper surface of the deposition plate 9; the thickness of the deposited film is realized by regulating and controlling the moving speed of the moving platform 14;
the deposition plate 9 is a flat metal conductive material (copper plate);
applying an electric field between the ion deflection/detection plate 8 and the electrode plate a to detect metal ions first, and then separating and depositing: during metal ion detection, the electric field direction is directed to the ion deflection/detection plate 8 by the deposition plate 9; during metal ion deposition, the electric field direction is directed from the ion deflection/detection plate 8 to the deposition plate 9.
A high-field asymmetric waveform voltage and a direct-current compensation voltage are applied to the high-voltage electrode 5, the frequency of the high-field asymmetric waveform voltage is 1MHz, and the integration areas of the high-field asymmetric waveform voltage and the low-field voltage in one period are equal to each other: the high field voltage is 4500V (duration 0.1 us), the low field voltage is 500V (duration 0.9 us); the DC compensation voltage is between-50V and 50V, and the scanning step length is equal to 0.1V;
when metal ions are detected, the radio frequency voltage is fixed, the direct current compensation voltage is scanned step by step, so that metal ions with different sizes pass through the ion screening area 12, the size distribution of the metal ions is obtained, and the direct current compensation voltage values corresponding to the peak signal intensities of the metal ions with multiple sizes are obtained; during deposition, the radio frequency voltage is fixed, and meanwhile, the direct current compensation voltage is fixed at a direct current compensation voltage value corresponding to a peak value signal, so that ions with the size pass through the ion screening area 12 only, and the screening of the ions with the size of a specific size is realized;
the width of the square through hole 3 in the Z axis direction is equal to the width of the corresponding high-voltage electrode 5 and the corresponding ground electrode 7;
the electrospray capillary 1 is applied with direct-current high voltage, the voltage amplitude is 5kV, and the electrode plate 2 is grounded.
The radiant heating source 4 may be an infrared heating lamp; the heating temperature of the area between the electrode plate 2 and the ion screening area is 150 ℃, and the heating temperature is regulated by adjusting the power of the radiation heating source 4;
the heating temperature of the heating plate 10 is 100 degrees celsius.
The specific implementation is as follows: a metal capillary tube with the inner diameter of 200um and the outer diameter of 3.2mm is adopted, and the inner diameter of the sleeve on the outer side is 3.5mm and the outer diameter is 5mm; the electrode plate 2 has dimensions of 2cm×5cm (length×width, Y axis and Z axis); the distance between the electrospray electrode 1 and the electrode plate 2 is 1.5cm; the opening size of the square through hole 3 is 0.5mm×5mm (length×width, Y axis and Z axis); ruler for high-voltage electrode 5 and ground electrode 7The dimension is 1.5cm multiplied by 1.5cm (length multiplied by width, X axis and Z axis), and the distance between the two is 0.5mm (Y axis); the ion deflection/detection plate 8 has dimensions of 2cm×2cm (length×width, X-axis and Z-axis); the deposition plate 9 has an area of 2cm×2cm (length×width, X-axis and Z-axis); the ion deflection/detection plate 8 and the deposition plate 9 were spaced apart (Y-axis) by 0.5mm. Preparing Pd and Cu metal atomic layer films by using an electrospray atomic layer vapor deposition film-making device: cu concentration of 0.5mol/L in electrospray capillary 1 3 (BTC) 2 A metal precursor (BTC=1, 3, 5-benzene tricarboxylic acid triethyl), wherein the spraying flow rate is 10nL/min, spraying is formed in a region between an electrospray electrode 1 and an electrode plate 2 with a square through hole 3 at the center under the action of an electric field (the temperature of the region between the electrode plate 2 and an ion screening region is 150 ℃), and solvent volatilization is realized under the heating of a halogen lamp 4; the ion screening area 12 is accessed through the square through hole 3 (the frequency of the high-field asymmetric waveform voltage applied to the high-voltage electrode 5 is 1MHz, the integration area of the high-field asymmetric waveform voltage and the low-field voltage with respect to time is equal in one period, the high-field voltage is 4500V (duration is 0.1 us), the low-field voltage is 500V (duration is 0.9 us), the direct-current compensation voltage is between-50V and 50V, and the scanning step length is equal to 0.1V); the metal cluster ions with different particle diameters can generate radial offset under the action of high and low electric fields, and the ions with specific sizes can pass through the ion screening area 12 by regulating and controlling the amplitude of the direct current compensation voltage; setting the voltage on the deposition plate 9 to 15V, and simultaneously connecting the detection plate 8 with a micro-current amplifier (model DDPCA-300), so that the electric field direction is directed to the ion deflection/detection plate 8 by the deposition plate 9, and corresponding distribution of metal clusters with different particle diameters can be obtained on the ion deflection/detection plate 8 (as shown in figure 2, metal cluster ions with two different particle diameter distributions exist, and corresponding direct current compensation voltage distribution is 7.6V (particle diameter is 1-3 nm) and 8.5V (particle diameter is 8-9 nm)); then, the compensation voltage was fixed at 8.5V, the voltage on the deposition plate 9 was set at-30V, the voltage on the ion deflection/detection plate 8 was set at 0V to perform metal film deposition of a specific size, and the stage 14 was moved at a constant speed of 0.1 mm/sec while maintaining the heating temperature of the heating plate 10 at 100 degrees celsius, and a metal film (film thickness of about 0.05 um) of the same particle diameter was obtained on the deposition plate 9, as shown in the left graph of fig. 3. Applying a radio frequency voltage to the high voltage electrode 5 and directlyWhen the flow compensation voltage was set to 0V, all the metal ions of the particle size were passed through the ion screening zone 12, the stage 14 was moved at a uniform speed of 0.1 mm/sec, the heating temperature of the heating plate 10 was maintained at 100 degrees celsius, and a metal film (film thickness of about 0.05 um) of the same particle size was obtained on the deposition plate 9, as shown in the right drawing of fig. 3.
Claims (10)
1. An electrospray atomic layer vapor deposition film forming device is characterized in that:
taking the left-to-right direction as an X-axis direction, taking the up-to-down direction as a Y-axis direction, and taking the directions perpendicular to the X-axis and the Y-axis as Z-axis directions;
the device comprises the following components from left to right: an electrospray electrode (1) formed by an electrospray capillary tube with an outer sleeve, an electrode plate (2) with a square through hole (3) at the center, an ion screening area (12) formed by a high-voltage electrode (5) and a ground electrode (7) which are oppositely arranged, an ion deflection/detection plate (8) and a deposition plate (9) which are oppositely arranged;
a radiation heating source (4) is arranged outside the gap between the electrode plate (2) and the ion screening area and is used for heating the area between the electrode plate (2) and the ion screening area; the deposition plate (9) positioned on one side of the ion screening area (12) far away from the electrode plate (2) can reciprocate along the X-axis direction or rotate parallel to the rotating shaft of the Z-axis.
2. The apparatus of claim 1, wherein:
the electrospray capillary needle is sleeved in the outer sleeve; the outlet of the electrospray electrode (1) faces the square through hole (3);
the high-voltage electrode (5) is connected with the high-voltage power supply (6); the ground electrode (7) is grounded;
positive high voltage is applied to an electrospray capillary needle of the electrospray electrode (1), the electrode plate (2) is grounded, and spray is formed in a region between the positive high voltage and the electrode plate; the metal precursor solution flows through the electrospray capillary, the carrier gas flows through the area between the inner wall surface of the outer sleeve and the outer wall surface of the electrospray capillary, and under the driving of the carrier gas, the metal ion clusters pass through the square through holes (3) to move towards the ion screening area (12);
the lower surface of the flat high-voltage electrode (5) and the upper surface of the flat ground electrode (7) below the flat high-voltage electrode are oppositely arranged, and an ion screening area (12) is formed between the flat high-voltage electrode and the flat ground electrode along the X-axis direction.
3. The apparatus of claim 1, wherein:
the deposition plate (9) is a flat plate, the upper surface of the deposition plate is parallel to the X axis, and the upper surface of the flat plate is parallel to the upper surface of the ground electrode (7), or the upper surface of the deposition plate is positioned below the plane of the upper surface of the ground electrode (7); a heating plate (10) for heating the deposition plate (9) is arranged at the lower part of the deposition plate (9), and the heating plate (10) is fixed on a movable platform (14) capable of reciprocating along the X-axis direction; an electric heating element (13) (such as one or more of an electric heating wire, an electric heating rod and an electric heating block) is arranged in the heating plate (10)
Or the deposition plate (9) is a columnar or cylindrical (such as a cylinder) axisymmetric body, the axis of the axisymmetric body is parallel to the Z axis, and the top of the columnar axisymmetric body is positioned on the plane or below the plane of the upper surface of the ground electrode (7); an electric heating element (13) (such as one or more of an electric heating wire, an electric heating rod and an electric heating block) for heating the deposition plate (9) is arranged inside the deposition plate (9); a rotating shaft is arranged in the columnar axisymmetric body along the axis of the columnar axisymmetric body in a penetrating way, one end of the rotating shaft is fixedly connected with or in transmission connection with an output shaft of a motor, and the columnar axisymmetric body is driven to rotate along the axis of the columnar axisymmetric body through the motor.
4. A device as claimed in claim 3, wherein:
when the deposition plate (9) is a flat plate, the lower part of the moving platform (14) is provided with rollers, so that the moving platform (14) can reciprocate along the X-axis direction; a temperature probe (11) or a temperature sensor is arranged in the heating plate (10);
or when the deposition plate (9) is a columnar axisymmetric body, one end of the rotating shaft is in transmission connection with an output shaft of a motor through a chain or a belt; a temperature probe (11) or a temperature sensor is arranged inside the deposition plate (9);
the temperature probe (11) or the temperature sensor is connected with the temperature controller; the electric heating element (13) is connected with an external power supply through a temperature controller.
5. The apparatus of claim 1, wherein:
the lower surface of the flat ion deflection/detection plate (8) is parallel to the X axis, and the lower surface of the flat ion deflection/detection plate is parallel to the lower surface of the high-voltage electrode (5) or the lower surface of the flat ion deflection/detection plate is positioned above the plane where the lower surface of the high-voltage electrode (5) is positioned;
the ion deflection/detection plate (8) is made of metal or an insulating sheet with a metal coating on the side facing the deposition plate (9), and the substrate is connected with a current detector.
6. A device as claimed in claim 1 or 3, wherein:
introducing liquid metal precursor solution into the electrospray capillary needle;
when the deposition plate (9) is a flat plate, the deposition plate (9) and the heating plate (10) move at a uniform speed along the X axis under the action of the moving platform (14) in the deposition process, so that a uniformly distributed metal film is obtained on the upper surface of the deposition plate (9); the thickness of the deposited film is realized by regulating and controlling the moving speed of the moving platform (14);
or when the deposition plate (9) is a columnar axisymmetric body, the deposition plate (9) rotates at a constant speed under the action of a motor in the deposition process, so that a uniformly distributed metal film is obtained on the surface of the deposition plate (9); the thickness of the deposited film is achieved by the rotational speed of the motor output.
7. The apparatus of claim 1 or 6, wherein:
when the deposition plate (9) is a flat plate, at least one of the deposition plate (9) and the heating plate (10) is made of conductive material (such as metal) as an electrode plate A; or when the deposition plate (9) is a columnar axisymmetric body, the deposition plate (9) is made of conductive material (such as metal) and is used as an electrode plate A;
applying an electric field between the ion deflection/detection plate (8) and the electrode plate A to detect metal ions firstly, and then separating and depositing: when metal ions are detected, the electric field direction is pointed to the ion deflection/detection plate (8) by the deposition plate (9); during metal ion deposition, the electric field direction is directed from the ion deflection/detection plate (8) to the deposition plate (9).
8. The apparatus of claim 1 or 2, wherein: applying a high-field asymmetric waveform radio frequency voltage and a direct current compensation voltage to the high-voltage electrode (5), wherein the frequency of the high-field asymmetric waveform radio frequency voltage is 0.1MHz to 100MHz, and the integration area of the high-field asymmetric waveform radio frequency voltage and the low-field voltage in one period is equal to time: the high field voltage is a fixed value in the range of 1000V to 10000V, and the low field voltage is a fixed value in the range of 100V to 500V; the DC compensation voltage is between-30V and-50V and between 30 and 50V (such as between-50V and 50V), and the scanning step length is less than or equal to 0.5V (such as 0.1-0.5V);
when metal ions are detected, the high-field asymmetric waveform radio frequency voltage is fixed, and the direct current compensation voltage is scanned step by step, so that metal ions with different sizes pass through an ion screening area (12), the size distribution of the metal ions is obtained, and the direct current compensation voltage value corresponding to the peak signal intensity of the metal ion groups with multiple sizes is obtained; during deposition, the high-field asymmetric waveform radio frequency voltage is fixed, and meanwhile, the direct current compensation voltage is fixed at a direct current compensation voltage value corresponding to a metal ion group peak signal with a required size, so that the ion group with the size only passes through an ion screening area (12) to screen the ion group with the specific size.
9. The apparatus of claim 1 or 2, wherein: the width of the square through hole (3) in the Z-axis direction is larger than or equal to the width of the corresponding high-voltage electrode (5) and the corresponding ground electrode (7);
and a direct-current high voltage is applied to the electrospray capillary (1), the voltage amplitude is 1kV to 10kV, and the electrode plate (2) is grounded.
10. The apparatus of claim 1, wherein:
the radiation heating source (4) can be one or more than two of an infrared heating lamp, an incandescent lamp, a halogen tungsten lamp and a halogen lamp; the heating temperature of the area between the electrode plate (2) and the ion screening area is between room temperature and 400 ℃, and the temperature is regulated by adjusting the power of the radiation heating source (4);
the heating temperature of the heating plate (10) ranges from room temperature to 300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311610980.2A CN117702086A (en) | 2023-11-29 | 2023-11-29 | Electro-spray atomic layer vapor deposition film making device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311610980.2A CN117702086A (en) | 2023-11-29 | 2023-11-29 | Electro-spray atomic layer vapor deposition film making device |
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| CN117702086A true CN117702086A (en) | 2024-03-15 |
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| CN202311610980.2A Pending CN117702086A (en) | 2023-11-29 | 2023-11-29 | Electro-spray atomic layer vapor deposition film making device |
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| CN (1) | CN117702086A (en) |
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- 2023-11-29 CN CN202311610980.2A patent/CN117702086A/en active Pending
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