JPS62274732A - Device for adhering thin film to substrate - Google Patents

Abstract

PURPOSE:To automatically adhere two types of molecular layers to the surface of a substrate by a method wherein a fixed barrier, a movable barrier, a movable barrier driving means, a substrate vertically driving means, and a substrate horizontally driving means are provided. CONSTITUTION:A fixed barrier 38 is attached in hanging on a disc 20 through the intermediary of a water-level regulating bolt 40, and the height of the surface S of the water 24 against the upper surface of the fixed barrier 38 is regulated by rotating the water-level regulating bolt 40 around its axis. A recessed part 50 is formed on a sector 46, and the high molecular solution floated on the surfaces S1 and S2, to be divided into two parts by a sector 40 and a movable barrier 58, is prevented from mixing by crossing the sector 46. The end part of the movable barrier 58 is mounted on the upper surfaces 52 and 56 of the edge part, and the area of the surfaces S1 and S2 is regulated by rotating the movable barrier 58 around the axial center of the center 44. A vertically moving arm 80 passes through an aperture 101, and it is rotated horizontally in the aperture 101.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Industrial Field of Application] The present invention provides a method for forming a thin film on a substrate, in which two types of molecular layers can be deposited on the surface of the substrate by the Langmuir-Blodgett method. Relating to a deposition device.

[Conventional technology]

In this type of thin film deposition device, a fixed barrier whose upper surface is in a substantially horizontal plane surrounds a part of the surface of the water in the container, a movable barrier is mounted on the upper surface of the fixed barrier, and the movable barrier is moved in the horizontal direction. By adjusting the area of the water surface divided by the fixed barrier and the movable barrier, a polymer solution (non-volatile, insoluble in water, containing both hydrophilic and hydrophobic groups in one molecule) floating on the ice surface was created. A monomolecular layer formed by diluting (dissolving) an amphiphilic substance, such as diethylene, in a water-insoluble and volatile solvent is made uniform, and a substrate is placed above and below the water surface. A single layer or multiple layers of sheep molecules are deposited on the surface of the substrate by moving the membrane (Japanese Patent Application Laid-open No. 35515/1983).

[Problem that the invention seeks to solve]

However, one M-mounted machine with thin film! Only one type of molecule can be attached to a substrate using a method, and in order to consecutively attach two types of molecules to a substrate, two thin film deposition devices are used, and the substrate is transferred from one device to the other. Clothes had to be changed manually to the machine.

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide an apparatus for depositing a thin film onto a substrate, which can automatically deposit two types of molecular layers onto the surface of the substrate.

[Means for solving problems]

In the thin film deposition apparatus on a substrate according to the present invention, there is provided a fixed barrier that surrounds a part of the liquid surface in a container and whose upper surface is in a substantially horizontal plane, and a fixed barrier that is in sliding contact with the upper surface of the fixed barrier and that is surrounded by the enclosed surface S. is divided into a surface S and a surface S2, and a polymer solution A floating on the surface S and a polymer solution B floating on the surface S2 are prepared.
A movable barrier that prevents mixing between the two and a movable barrier drive that adjusts the areas of the surfaces S+ and Sz by sliding the movable barrier and uniformizes the single molecules III M+ -Mz formed by the polymer solutions A and S. means for moving the substrate up and down the surface S to deposit the monomolecular layers M + and M z on the substrate surface; A horizontal drive means for moving the substrate.

[Effect]

Polymer solutions A and [3 are dropped onto surfaces S1 and S2, respectively, to form monomolecular layers M1 and Mt. The monolayer M, is made uniform by moving the movable barrier and reducing the area of the surface Sl. Next, the substrate is moved up and down (diagonally up and down or vertically up and down) on the surface S+ by the substrate up and down drive means. This causes a monomolecular layer M to adhere to the substrate surface. Depending on the number of vertical movements, the monomolecular layer M temporarily adheres to the base,
The number of layers is different.

Next, the substrate is moved in a substantially horizontal direction from the surface 31 side to the surface 82 side by the substrate horizontal movement means inside or outside the liquid in the container. Next, the substrate is moved to the surface S2 by the substrate vertical drive means.
Move it up and down (diagonally up and down or vertically up and down). This causes a monomolecular layer M2 to adhere to the substrate surface. The number of monomolecular layers M2 attached to the substrate varies depending on the number of vertical movements.
[Embodiment] A preferred embodiment of the apparatus for depositing a thin film on a substrate according to the present invention will be described with reference to the drawings.

FIG. 1 is a cutaway perspective view of the thin film deposition device 10, FIG. 2 is a plan view of the thin film deposition device 10, FIG. 3 is a sectional view taken along the line ■-■ in FIG. 2, and FIG. 4 is a IV of FIG. -r'/ line sectional view.

Receiving rings 14, 16 are protruded from the inner wall of the housing 12, and the peripheral edges of the container 18 and the disc 20 are placed on each of the receiving rings 14, 16, respectively. A part of the bottom of the container 18 protrudes downward to form a film forming part 22, so that the entire substrate 23 can be immersed in water 24 inside the container 18. On the bottom surface of the housing 12, an inner wall 2 is erected on the outer wall 26 side, and an outer chamber 36 is formed between the outer wall 26 and the inner wall 28, thereby providing a heat insulating structure. The inner wall 28 has an inlet pipe 30
An outlet pipe 32 is provided protruding from the outer wall 26, and hot or cold water is discharged from the outlet pipe 32 through the inlet pipe 30, through the inner chamber 34 and the outer chamber 36, and drains the water 24 in the container 18. It is designed to maintain a predetermined temperature.

A fixed barrier 3 is attached to the disk 20 via a water level adjustment bolt 40.
8 is suspended, and the height of the surface S of the water 24 relative to the upper surface of the fixed barrier 38 is adjusted by rotating the water level adjustment bolt 40 about its axis. The fixed barrier 38 is integrally molded, and the outer ring 42
It has a center 44, a sector 46 and spokes 47 and 49 that connect these. A recess 48 is formed in the center of the center 44 to reduce the contact area between the edge upper surface 52 and the movable barrier 58 to reduce frictional force. A recess 50 is also formed in the sector 46 to prevent the polymer solution floating on the surfaces S1 and St divided into two by the sector 46 and the movable barrier 58 from mixing beyond the sector 46. Top surface 56 of ring 42, edge top surface 54 of sector 46 and center 4
4 are on the same plane, and there is no water 24 on these surfaces, but by using the surface tension of the water 24, the surface S of the water 24 is slightly higher than these surfaces. The water level is adjusted by the water level adjustment bolt 40 so that the water level becomes the same. The spokes 47,49 are for reinforcement and their upper surfaces are lower than the edge upper surface 52 of the sector 46 so as not to divide the surface S of the water 24.

The ends of a movable barrier 58 are mounted on the upper edge surfaces 52 and 56, and by rotating the movable barrier 58 around the axis of the center 44, the areas of the surfaces S, , sz are adjusted. ing.

One end of a 0-shaped metal fitting 62 is fixed to the base end surface of the movable barrier 58. The 0-shaped metal fitting 62 is loosely held by a holding piece 64, and a reducer and shaft 70 (not shown) are driven by a motor 68 built in a rotating device 66.

It is designed to be rotationally driven through. Rotating device 66
is fixed to the upper surface of the disc 20.

A rotating arm 72 is protruded from the side surface of the rotating device 66, and is driven to rotate about an axis 76 by a motor 74 via a speed reducer (not shown). A lifting device 78 is fixed to the tip of the rotating arm 72. A lifting arm 80 vertically passes through the lifting device 78, and is lifted and lowered using a ball screw. That is, a protruding piece 82 is provided on the side surface of the elevating arm 80, and a screw 84 pivotally supported by the elevating device 78 is attached to the protruding piece 82.
2 is made of wax, and this screw shaft 84 connects to the motor 86.
The lifting arm 80 is rotated and moved up and down. A steel ball is fitted into a groove formed by the protruding piece 82 and the male and female threads of the screw shaft 84 facing each other, so that the elevating arm 80 moves up and down smoothly. A magnetic drive clip 88 is provided at the lower end of the lifting arm 80, and a solenoid (not shown) moves the board 23.
It is designed to clamp or release the clamping. Further, in the same manner as described above, a swing arm 90 is vertically passed through the tip of the lifting device 78, and is lifted and lowered using a ball screw. That is, a protruding piece 96 is provided on the side surface of the vertical portion 92 of the swing arm 90, and a screw shaft 98 that is rotatably supported on the elevating device 7 attaches this protruding piece 96, and this screw shaft 98 is rotated by the motor 100. The swing arm 90 is driven to move up and down. A steel ball is fitted into a groove formed by the protruding piece 96 and the male and female threads of the screw shaft 98 facing each other, so that the swing arm 90 moves up and down smoothly. The lower end of the swing arm 90 is bent to form a horizontal portion 94, and two opposing clamping pieces 102 are protruded from the upper surface of the horizontal portion 94. The board 23 is held by the clamping piece 102
．． When held between the substrates 102, the upper end of the board 23 will not fall down even if it is not held by the magnetically driven clips 88.

An opening 101 having substantially the same shape as the bottom surface of the film forming section 22 is bored in the disk 20 above the film forming section 22 . The elevating arm 80 passes through this opening 101, and the elevating arm 80 can be pivoted horizontally within the opening 101. On both sides of this opening 101, the disk 20 has a surface S,
A surface pressure sensor 104 is fixed on the side, and a surface pressure sensor 105 is fixed on the surface 82 side.

The surface pressure sensors 104 and 105 have the same configuration and are designed to detect pressure on the surface S in the horizontal direction. The surface pressure sensor 105 is a fixed cylindrical differential transformer 1.
06 is fitted with a movable iron core 10B. Movable iron core 10
The upper end of 8 is connected to the lower end of an adjusting screw 114 via a coil spring 110. A two-round screw 114 is screwed onto the racket 112S. A Wilfermi plate 118, such as a filter paper, is suspended from the lower end of the movable core 108 via a hook 116. Therefore, the movable core 108 moves in the vertical direction due to a change in the pressure in the substantially horizontal direction on the surface S, and this is detected by the differential transformer 10G, and this pressure can be read.

Note that the disk 20 is made of a transparent material, so that the bottom thereof can be visually observed. Furthermore, the ring 42 and the movable barrier 58 are made of a material that is hydrophobic and has a small coefficient of friction, such as PTFE (polytetrafluoroethylene), and forms a stable R-shaped boundary between the water 24 and the fixed barrier 38. At the same time, the movable barrier 58 can smoothly rotate on the fixed barrier 38.

Next, how to use the thin film deposition apparatus 10 configured as described above will be explained.

Place the peripheral edge of the container 18 on the receiving ring 14, and
Put 24ml of water inside. The hot water or cold water is returned to W1 through the inlet pipe 30 and the outlet pipe 32, and the water 24 is kept at a predetermined temperature (room temperature ±
(within 10℃). circle? Water level adjustment bolt 4 on J120
A fixed barrier 38 is hung through the 0. The upper surface 56 is filled with water 2
Adjust the water level adjustment bolt 40 so that it is located below the surface S of the disc 20,
Place it on top. Note that the rotating device 66, surface pressure sensors 104, 105, etc. are already attached to the disk 20. The lifting arm 80 is raised to the upper limit position, and the upper end of the board 23 is held by the magnetically driven clip 88. Next, the movable barrier 58 is positioned above the recess 50. The water level adjustment bolt 40 is then adjusted to raise the fixed barrier 38 and the water on the top surface 52, 54, 56 is repelled and removed. At this time, the surface S is slightly higher than the upper surface 56. Next, the motor 68 is turned on to rotate the movable barrier 58 once, thereby sweeping away the surface S of the water 24. Dirty water enters the recess 48 of the sector 46. Furthermore, the movable barrier 58 is rotated by half a rotation and stopped at the position Po shown in FIG.

Next, different polymer solutions A and B are dropped onto the surfaces S, , S, respectively. This polymer solution is nonvolatile and insoluble in water, and uses an amphiphilic substance as a solute that contains both hydrophilic and hydrophobic groups in the molecule, and is used by dissolving it thinly in a primary solvent that is insoluble in water. be done. This dripping causes the surface S
1. A monolayer is formed on Sz. In particular, OH, C0OH, So, 5O3 as a hydrophilic group at one end of a long hydrocarbon chain.
A stable monomolecular layer is formed in the case of molecules with H or the like bonded to them.

Specific examples of amphiphilic substances include combinations of various phthalocyanines that form the charge generating layer and oxazole or hydrazone molecules that are laminated on the layer to form the charge transport layer. By providing electrodes on both sides of such a laminated layer, a photoreceptor can be constructed, which is used for electrophotographic photosensitive materials, photoelectric conversion elements, and the like.

Next, the motor 74 is turned on, and the lifting device 78 is rotated to the line P1 shown in FIG. 2 and stopped. Next, the movable barrier 58 is rotated counterclockwise in FIG. As a result, the pressure in the substantially horizontal direction on the surface Sl increases, and the movement of the movable barrier 58 is continued to be controlled by the motor 68 so that the pressure detected by the surface pressure sensor 104 becomes a predetermined value. This forms a uniform monolayer on the surface Sl.

Next, the motor 86 is turned on to move the substrate 23 up and down the surface S1. The substrate 23 rises or falls to the surface S,
When traversing, the monomolecular layer M, on the surface Sl adheres to the substrate 23, and the monomolecular layer M, is formed on the surface of the substrate 23. If the lifting arm 80 is moved back and forth N times in the vertical direction, the substrate 230
A monomolecular layer M1 of 2NJi will be deposited on the surface. This attachment prevents the distribution density of single molecules FJMI on the surface S from becoming small. That is, the movable barrier 58 is further controlled to rotate in the counterclockwise direction in FIG. At the same time, the motor 86 is turned on to lower the elevating arm 80, and the lower end of the substrate 23 is held between the holding pieces 102.

Then, the upper end of the substrate 23 is released from being held by the magnetic drive clip 88.

Next, the lifting arm 80 is raised to the upper limit position, and the swing arm 90 is lowered to the lower limit position.

As a result, the entire substrate 23 is immersed in the water 24, and the upper end of the substrate 23 is located below the lower surface of the recess 50. Next, the motor 74 is turned on, and the rotary arm 72 is rotated counterclockwise in FIG. 1 about the axis 76 to the position of line P2 shown in FIG. 2, and then stopped. Next, the motor 68 is turned on to rotate the movable barrier 5B clockwise in FIG. 1, and the rotation of the movable barrier 58 is always controlled so that the pressure detected by the surface pressure controller 105 becomes a predetermined value. This forms a uniform monolayer M2 on the surface S2. Next, the motor 86.100 is turned on, the lifting arm 80 is lowered and the swinging arm 90 is raised, the upper end of the board 23 is held between the magnetically driven clips 88, and the swinging arm 9 is lowered.
0 to the lower limit position. Next, the lifting arm 8o is raised and lowered to move the substrate 23 above and below the surface S2, and the single molecule 1iiMz on the surface S2 is attached to the surface of the substrate 23 in the same manner as described above.

By repeating the above process, a molecular layer consisting of two types of molecules can be laminated and adhered to the surface of the substrate 23.

Here, the way the monomolecular layer is attached to the substrate 23 differs depending on the type of amphiphilic substance that is the solute of the polymer solution.
There are the following:

■When the substrate 23 is put into the water 24, the monomolecular layer is removed from the substrate 2.
3, but not when the substrate 23 is removed from the water 24.

■When the substrate 23 is taken out of the water 24, the monomolecular layer is removed from the substrate 2.
3, but not when the substrate 23 is placed in the water 24.

(2) A monomolecular layer is deposited on the substrate 23 when the substrate 23 is put into the water 24 and taken out from the water 24.

Regarding (2) and (2) above, even if two conventional thin film deposition apparatuses are used, different types of monomolecular layers can be deposited layer by layer onto the substrate 23 (heterostructure film).

However, regarding item (2) above, such adhesion cannot be achieved even if two conventional devices are used. In the apparatus of this embodiment, the substrate 23 can be moved from the lower side of the surface Sl or St to the lower side of the other surface 32 or Sl while keeping the substrate 23 immersed in the water 24. 2
This has the advantage that different monolayers can be deposited layer by layer onto 3.

In addition, for the above (■) and (2), when a different type of monomolecular layer is deposited on the substrate 23 for each layer or multiple layers, or for the above (2), a different type of monomolecular layer is deposited for each even number of layers on the substrate 23. In this case, the board 23 is placed above the sector 46 with the upper end of the board 23 held between the magnetically driven clips 88.
The lower end of
8 may be rotated.

Alternatively, the fixed barrier 38 may have a rectangular ring 42, no center 44 and no sector 46, and both ends of the movable barrier 58 may be mounted on opposite sides of the fixed barrier so that the movable barrier 58 can be slid.

Next, another example of the surface pressure sensor used in the thin film deposition apparatus will be described with reference to FIG.

In this surface pressure sensor 200, a Will Fermi plate 118 is suspended from one end of a bar 204 by a thread 202. A wire 206 is fixed through the middle portion of the bar 204 . Both ends of the wire 206 are fixedly supported by end faces of supports 208 and 210, respectively. A worm wheel is formed on the support 208 and meshes with the adjustment worm 212 . These supports 2
8.210, the adjustment worm 212 is pivotally supported in a housing not disclosed.

A conductor 218 is suspended from the other end of the bar 204 by a thread 216. The electrical conductor 218 is a differential transformer 220
It is loosely fitted into the air core part of the eddy current type high frequency differential transformer.
The detector is configured.

This differential transformer 220 is fixed to the housing.

Therefore, when the lower part of the Wilfermi plate 118 is immersed in water 24, the Wilfermi plate 11
8 is a bar 20 under pressure in a substantially horizontal direction from the surface S.
A counterclockwise moment in FIG. 5 acts on bar 2. This moment is balanced by a clockwise moment in FIG. 5 due to the weight of the conductor 218 and the twisting of the wire 206.
04 is tilted at a predetermined angle. At this time, the conductor 218 moves in the vertical direction, the impedance of the differential transformer 220 changes, and the substantially horizontal pressure received from the surface S is detected.

In this surface pressure sensor 200, even if the movement of the movable barrier 58 causes a flow on the water surface, which causes the Wilfermi plate 118 to move in the horizontal direction and the thread 202 to tilt, the thread 216 does not tilt. 218 comes into contact with the inner circumferential surface of the differential transformer 220 and the conductor 218 does not move up and down discontinuously, and the pressure can be detected as a positive value. This has the effect of making it possible to deposit molecular layers.

This effect is further enhanced by the fact that the magnetic force that the conductor 218 receives from the differential transformer 220 is sufficiently smaller than the magnetic force that the movable core 10 shown in FIG. 4 receives from the differential transformer 106.

Note that the mechanical zero point adjustment of the surface pressure sensor 200 is performed by rotating a knob 214 provided at the upper end of the adjustment worm 212.

(Effects of the Invention) In the thin film deposition device on a substrate according to the present invention, the surface S surrounded by the fixed barrier is divided into the surface S1 and the surface S2 by the movable barrier, and the polymer solution A floating on the surface S1 is divided into the surface S1 and the surface S2 by the movable barrier. The single molecules formed by the polymer solutions A and B are prevented from mixing with the polymer solution B floating on the surface S2, and the movable barrier is slid on the upper surface of the fixed barrier to adjust the area of the surfaces S1 and Sz. The layers Ml and M2 are made uniform, the substrate is moved approximately horizontally from one of the surfaces S1 and S2 by the substrate horizontal drive means, and the substrate is moved up and down the surfaces S, , SZ by the substrate vertical drive means. Since the monomolecular layers M + and M z are deposited on the substrate surface using a single film deposition device, monomolecular layers consisting of two or more types of molecules can be deposited alternately and continuously onto the substrate using a single film deposition device. It has the excellent effect of being able to be adhered to the target surface.

[Brief explanation of drawings]

1 is a cutaway perspective view of a thin film deposition apparatus according to an embodiment of the present invention, FIG. 2 is a plan view of the thin film deposition apparatus, FIG. 3 is a sectional view taken along the line ■-■ of FIG. IV-rV line sectional view of the figure,
FIG. 5 is a perspective view showing another example of the surface pressure sensor. 23...Substrate 38...Fixed barrier 40...Water level adjustment bolt 58...Movable barrier 66...Rotating device 7th...Elevating device

Claims (1)

[Claims] a fixed barrier that surrounds a part of the liquid surface in the container and whose upper surface is in a substantially horizontal plane; A movable barrier prevents the polymer solution A floating on the surface S_2 from mixing with the polymer solution B floating on the surface S_2, and the movable barrier is slid to adjust the areas of the surfaces S_1 and S_2, and the polymer solution A, A movable barrier driving means that makes the monomolecular layers M_1 and M_2 formed by B uniform, and a movable barrier driving means that moves the substrate up and down the surface S to form a monomolecular layer M_2 on the substrate surface.
1. A thin film on a substrate characterized by having a substrate vertical drive means for adhering M_2, and a substrate horizontal drive means for moving the substrate from one of the surface S_1 side and the surface S_2 side in a substantially horizontal direction to the other. Adhesion device.