Method and apparatus for forming a film

• US 5,064,520 A
• Filed: 02/14/1990
• Issued: 11/12/1991
• Est. Priority Date: 02/15/1989
• Status: Expired due to Fees

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Nakagawa, Yukio, Miyake, Kiyoshi, Warabisako, Terunori, Isogai, Masato, Seki, Takayoshi, Arimatsu, Keiji, Natsui, Kenichi, Ouhata, Koukichi, Ohno, Yasunori
• Primary Examiner(s): Nguyen, Nam X.
• Application Number:
  US07/480,131
• Time in Patent Office: 636 Days
• Field of Search: 204/192.11, 204/192.12, 204/298.04, 204/298.02, 204/298.23, 204/298.07, 427/38, 427/53.1
• US Class Current: 204/192.11
• CPC Class Codes: C23C 14/12 Organic material
• CPC Class Codes: C23C 14/3407 Cathode assembly for sputtering apparatus, e.g. Target
• CPC Class Codes: C23C 14/3414 Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

Abstract

This invention relates to a method and an apparatus for forming a film, which are suitable for forming a film of a semiconductor, dielectric, metal, insulator, or organic substance. In order to form a film of high purity and quality at high speed, a particle beam such as an ion beam, an electron beam, or a plasma is applied to a sputtering target comprising a substance formed by bonding atoms or molecules with either van der Waals forces or hydrogen bonding forces, the particles are sputtered thereby from the target, fly in the space in the vacuum chamber, reach the substrate on which they are deposited to form a desired film. To form an organic film free of pinholes, impurities, or disorder in the molecular composition and arrangement in a large area at high speed, a particle beam of about 10 eV or less is applied to the target comprising an organic compound disposed in a vacuum, the particle beam having a level of energy as high as can break the molecular crystalline bonds and not high enough to break the nonmolecular crystalline bonds, out of the molecular crystalline bonds by van der Waals forces connecting the atoms constituting the organic compound and the nonmolecular crystalline bonds by covalent bonds, for example, other than van der Waals forces, and the sputtered particles from the target are deposited on the substrate facing the target to form a desired film of an organic compound.

Claims

1. A method of forming a film, comprising the steps of:

applying a particle beam to a material substance bonded by either van der Waals forces or hydrogen bonding forces, so as to sputter particles from said material substance, thereby producing particles from the material substance by sputtering;

applying the particles produced by sputtering of said material substance to a substrate; and

forming a film, including at least the particles produced by the sputtering, on said substrate.

2. The method according to claim 1, wherein at least a part of the particles produced by said sputtering are ionized to ions by electron impact or laser light means, and wherein a film is formed by including at least a part of the ions or applying both the ions and said sputtered particles to a substrate.

3. The method according to claim 1, further comprising the step of controlling an external shape of the material substance bonded by either van der Waals forces or hydrogen bonding forces by applying a laser light to a region of the material substance and by partially evaporating said material substance of the region to which the laser light was applied.

4. The method according to claim 1, wherein the particle beam is applied to the material substance, and the particles produced by sputtering are applied to the substrate, in a vacuum.

12. The method according to claim 1, 5, 8, 10 or 11, further comprising the step of accelerating the film forming process on the surface of said substrate by heating, or by applying another exciting beam selected from the group consisting of an ion beam, electron beam, radicals or light.

5. A method for forming a film, comprising the steps of:

having a material substance adsorbed on a target held at a temperature below the melting point of the material substance, said material substance being bonded, as adsorbed on the target, by van der Waals forces or hydrogen bonding forces;

sputtering said material substance bonded by either van der Waals forces or hydrogen bonding forces by applying a particle beam thereto, so as to form sputtered particles; and

applying the sputtered particles produced by said sputtering to a substrate to form a film thereon.

6. The method according to claim 5, wherein at least a part of the particles produced by said sputtering are ionized to ions by electron impact or laser light means, and wherein a film is formed by including at least a part of the ions or applying both the ions and said sputtered particles to the substrate.

7. The method according to claim 5, wherein the sputtering, and the applying the sputtered particles to the substrate, are performed in a vacuum.

8. A method for forming a film in a space having a vacuum therein, comprising the steps of:

introducing a material substance for a film into the space having the vacuum;

solidifying said material substance in the space, by having it come into contact with and adsorbed on the surface of a target cooled to below the melting point of the material substance, so as to form solidified material substance on the target, the solidified material substance being bonded by van der Waals forces or hydrogen bonding forces;

sputtering with an ion beam the solidified material substance;

forming on the substrate a film including at least a part of said material substance therein by applying sputtered particles produced by said sputtering to said substrate.

9. The method according to claim 8, wherein the sputtering, and the applying the sputtered particles to the substrate, are performed in a vacuum.

10. A method for forming a film in a vacuum chamber, comprising the steps of:

solidifying a material substance for a film, by cooling said materials substance to below its melting point in a place separate from a vacuum chamber in which the film is formed, so as to form a solidified material substance, the solidified material substance being bonded by van der Waals forces or hydrogen bonding forces;

introducing said solidified material substance into said vacuum chamber, into a vacuum;

sputtering the solidified material substance introduced into the vacuum by an ion beam; and

applying sputtered particles produced by said sputtering to a substrate to form on said substrate a film including at least a part of said material substance.

11. A method for forming a film, comprising the steps of:

introducing into a vacuum at least two kinds of material substance for a film;

preparing a cooling target cooled in the vacuum, cooled to a temperature lower than the melting point of any of the material substances introduced into the vacuum;

bringing said material substances into contact with the surface of said cooling target, held at the temperature lower than the melting point of any of the material substances introduced into the vacuum, to form a solidified layer of a mixture of said at least two kinds of said material substance, the solidified layer being bonded by van der Waals forces or hydrogen bonding forces;

sputtering particles from said solidified layer by applying a particle beam to said solidified layer; and

applying said sputtered particles to a substrate in the vacuum, to form a film thereon.

13. A method for forming a film, comprising the steps of:

applying a particle beam to at least two material substances each bonded by either van der Waals forces or hydrogen bonding forces, the at least two material substances respectively being provided at at least two places to provide, respectively, at least two places respectively for generating sputtered particles from said at least two material substances by sputtering;

simultaneously or intermittently controlling the time for sputtering at the at least two places to generate sputtered particles at the at least two places; and

forming on a substrate a film comprising the at least two material substances or a multilayered film respectively containing at least one material substance of the at least two material substances.

14. The method according to claim 13, wherein the particle beam is applied to the at least two material substances, and the film is formed on the substrate, in a vacuum.

15. A method for forming a film, comprising the steps of:

introducing at least two material substances for a film into a chamber;

solidifying said at least two material substances in the chamber, by having the at least two material substances come into contact with and be adsorbed on a surface of a target cooled to below the melting point of the at least two material substances, the at least two material substances, as solidified, each being bonded by either van der Waal forces or hydrogen bonding forces, the at least two material substances respectively being provided at at least two places;

sputtering with at least one ion beam the at least two material substances, solidified on said target at at least two places, to provide at least two places respectively for generating sputtering particles from said at least two material substances by sputtering;

simultaneously or intermittently controlling the time for sputtering at the at least two places to generate sputtered particles at the at least two places; and

forming on a substrate a film comprising the at least two material substances or a multilayered film respectively containing at least one material substance of the at least two material substances.

16. The method according to claim 15, wherein the solidified material substances are sputtered by an ion beam, and the film is formed on the substrate, in a vacuum.

17. A method for processing a substrate, comprising the steps of:

applying a particle beam to a substance bonded by van der Waals forces, so as to sputter particles from said substance, thereby forming sputtered particles from said substance; and

applying the sputtered particles, generated by sputtering of said substance, to a substrate material selected from the group consisting of a metal, dielectric, organic substance and semiconductor, to process said substrate.

18. The method according to claim 17, wherein the particle beam is applied to the substance, and the sputtered particles are applied to the substrate material, in a vacuum.

19. An apparatus for forming a film, comprising:

a vacuum chamber;

material substance introducing means for introducing into said vacuum chamber a material substance for a film, which is in gaseous or liquid state;

a target, held at a temperature below the melting point of the material substance introduced by said material substance introducing means, for forming on the surface of the target a layer, bonded by either van der Waals forces or hydrogen bonding forces, of said introduced substance;

a particle beam source for applying a particle beam to said layer bonded by either van der Waals forces or hydrogen bonding forces to sputter said layer; and

a substrate to which the particles, sputtered by a sputtering action by a particle beam from said particle beam source, are applied to form on the surface thereof a film including at least a part of said material substance.

23. The apparatus according to claim 19, 20, 21 or 22, further comprising a heating device for heating said substrate to accelerate the film forming process at the surface of said substrate.

24. The apparatus according to claim 19, 20, 21, or 22, further comprising exciting beam irradiation means for applying an exciting beam, selected from the group consisting of an ion beam, electron beam, radicals, and light, to accelerate the film forming process at the surface of said substrate.

25. The apparatus according to claim 19, 20, 21, or 22, further comprising a cooling panel, provided in said vacuum chamber, which is at a temperature lower than a temperature of a target for forming a layer bonded by either van der Waals forces or hydrogen bonding forces or a solidified layer and which is used to adsorb and trap a gas unnecessarily evaporating from a layer of material substance.

26. The apparatus according to claim 19, 20, 21, or 22, further comprising means for rotating or linearly reciprocating a cooler head for uniformly producing the layer bonded by either van der Waals forces or hydrogen bonding forces.

27. The apparatus according to claim 19, 20, 21, or 22, further comprising in said vacuum chamber a molecular beam evaporation device, a vacuum evaporation device, or an ionized cluster beam evaporation device for vapor-depositing a desired substance on said substrate.

20. An apparatus for forming a film, comprising:

a vacuum chamber;

material substance introducing means for introducing into said vacuum chamber a material substance for a film;

a target, cooled to below the melting point of the material substances to be introduced by the material substance introducing means, for adsorbing on the surface thereof a gas or a liquid substance introduced by said material substance introducing means, so as to form on the surface thereof material substance bonded by van der Waals forces or hydrogen bonding forces;

a charged particle source for applying charged particles to said target for sputtering said material substance, bonded by van der Waals forces or hydrogen bonding forces, on the target; and

a substrate to which particles sputtered by charged particles from said charged particle source are applied to form a film on the surface thereof.

21. An apparatus for forming a film, comprising:

a vacuum chamber;

material substance introducing means for introducing into said vacuum chamber a material substance for a film, which is in gaseous or liquid state;

a target, held at a temperature below the melting point of the material substance introduced by said material substance introducing means, for forming on the surface thereof a layer, bonded by van der Waals forces or hydrogen bonding forces, of the introduced material substance;

an ion source for applying an ion beam to said layer bonded by either van der Waals forces or hydrogen bonding forces to sputter said layer; and

a substrate to which particles sputtered by a sputtering action by an ion beam from said ion source, are applied to form on the surface thereof a film including at least a part of said material substance.

22. An apparatus for forming a film, comprising:

a vacuum chamber;

at least two material substance introducing means for separately introducing at least two material substances for a film into said vacuum chamber;

at least two targets, respectively held at temperatures below the melting points of the at least two material substances introduced separately by said at least two material substance introducing means, for forming on the surface of each target a layer of a respective introduced material substance, the layer being bonded by either van der Waals forces or hydrogen bonding forces;

at least two particle beam sources for simultaneously or intermittently applying particle beams to the layers, bonded by either van der Waals forces or hydrogen bonding forces, on said at least two targets, for sputtering particles from the layers; and

a substrate on which a multi-element film or a multilayered film is formed of particles which are sputtered from said at least two targets, when particle beams from said at least two particle beam sources are applied to the targets simultaneously or intermittently.

28. A method for forming a film comprising the steps of:

generating sputtered particles by sputtering of a material substance bonded by either van der Waals forces or hydrogen bonding forces by applying a particle beam to said material substance;

simultaneously and continuously supplying said material substance from outside; and

applying to a substrate said sputtered particles while maintaining the quantity of said material substance bonded by either said van der Waals forces or hydrogen bonding forces at a fixed level at all times to form on said substrate a film including at least a part of said material substance.

29. The method according to claim 28, wherein the sputtered particles are generated, and applied to the substrate, in a vacuum.

30. A processing apparatus, comprising:

a vacuum chamber;

introducing means for introducing into said vacuum chamber a substance, which is in a gaseous or liquid state;

a target, held at a temperature lower than the melting point of the substance introduced by said introducing means, for forming on the surface thereof a solidified layer of said introduced substance, the solidified layer of the introduced substance being bonded by either van der Waals forces or hydrogen bonding forces;

a particle beam source for applying a particle beam to the solidified layer of said target for sputtering particles of the solidified layer bonded by either van der Waals forces or hydrogen bonding forces; and

a substrate material, selected from the group consisting of a metal, dielectric, organic substance, and semiconductor, which is processed by application thereto of sputtered particles produced by sputtering of said solidified layer which occurs when a particle beam is applied to said solidified layer from said particle beam source.

31. A method for forming a film in a vacuum, chamber, comprising the steps of:

applying to a target of an organic compound a particle beam having a level of energy sufficient to break molecular crystalline bonds and not sufficient to break nonmolecular crystalline bonds of the organic compound, so as to sputter particles of the organic compound, the molecular crystalline bonds being bonds by van der Waals forces connecting the atoms constituting the organic compound and the nonmolecular crystalline bonds being bonds by other than van der Waals forces, so as to form sputtered particles from the target; and

depositing sputtered particles of said target on the surface of a substrate to form a film thereon.

33. The method according to claim 31 or 32, wherein said target is made by introducing into a vacuum a material substance which is in a gaseous or liquid state, and by adsorbing and solidifying said introduced material substance on the surface of a cooling head cooled to below the melting point of the material substances.

32. A method for forming a film in a vacuum chamber, comprising the steps of:

putting a target comprising an organic compound having molecular and nonmolecular crystalline bonds in the chamber;

applying a particle beam with energy of about 10 eV or less to said target comprising said organic compound, so as to break the molecular crystalline bonds and not break the nonmolecular crystalline bonds, and to form sputtered particles of the organic compound; and

depositing sputtered particles of said organic compound on the surface of a substrate to form a film thereon.

34. The method according to claim 32, wherein the particle beam applied has energy in the range of 6-10 eV.

35. An apparatus for forming a film, comprising:

a vacuum chamber;

a target disposed in said vacuum chamber and comprising an organic compound; and

a particle beam source for generating a particle beam, having energy of about 10 eV or less, to apply to said target, wherein particles are sputtered from said target by said particle beam generated by said particle beam source and are deposited on the surface of a substrate to form a film thereon.

36. The apparatus according to claim 35, wherein the particle beam source is for generating a particle beam having energy of 6-10 eV.

37. Apparatus for forming a film, comprising:

a vacuum chamber;

a target disposed in said vacuum chamber;

a particle beam source for generating a particle beam to apply to said target;

an organic compound introducing mechanism for introducing into the vacuum chamber an organic compound which is in gaseous or liquid state; and

a cooling head for cooling and holding said introduced organic compound at a temperature below the melting point thereof to form a solidified layer of said organic compound by adsorbing and solidifying said organic compound, wherein a particle beam generated by said particle beam source is applied to said solidified layer as the target to sputter said layer to deposit said sputtered particles on said substrate to form a film thereon.

38. The apparatus according to claim 37, further comprising a laser light generator for laser light irradiation of said target.

39. The apparatus according to claim 37, wherein said organic compound introducing mechanism communicates at one end with a pressure and temperature control section capable of controlling the pressure and temperature of an organic compound and has at the other end an organic compound introducing pipe provided with a blowout nozzle.

40. An apparatus for forming a film, comprising:

a vacuum chamber;

a target disposed in said vacuum chamber;

a particle beam source for generating a particle beam to apply to said target;

a substrate on which particles, ejected from said target by sputtering upon applying said particle beam to said target, are deposited to form a film;

an organic compound introducing mechanism for introducing into a vacuum an organic compound; and

a cooling head for cooling and holding said introduced organic compound at a temperature below the melting point thereof, so as to form a layer of the organic compound thereon in a solidified state, wherein said cooling head is formed in a columnar or cylindrical shape, and wherein an arrangement is made such that said substrate is movable in a direction substantially parallel with said cooling head, wherein the solidified layer of the organic compound is formed as a target on said cooling head, a particle beam from said particle beam source is applied to said target, and while said substrate is moved, a film of organic compound is formed on said substrate.

41. The apparatus according to claim 40, wherein said columnar or cylindrical cooling head is provided with a mechanism to rotate said cooling head about an axis thereof.

42. An apparatus for forming a film, comprising:

a vacuum chamber;

an introducing pipe for introducing into said vacuum chamber a gas as a material for a particle beam;

a cooling plate for cooling and holding a material gas introduced by said introducing pipe below the melting point of said material gas, and also for forming on the surface thereof a solidified layer of said material gas, the solidified layer being bonded by van der Waals forces or hydrogen bonding forces;

an ion source for applying ions to the solidified layer of said material gas, formed on the surface of said cooling plate, to eject sputtered particles from the solidified layer; and

an opening, provided at a part of said vacuum chamber, for taking out particles sputtered by said ion source, wherein a film forming chamber is provided which communicates with said opening of said vacuum chamber and is adapted to include a substrate therein, and wherein a film is formed on said substrate in said film forming chamber by utilizing particles sputtered by said ion source.