Method of manufacturing semiconductor device, acid etching resistance material and copolymer

• US 20050233483A1
• Filed: 02/14/2005
• Published: 10/20/2005
• Est. Priority Date: 03/31/2004
• Status: Active Grant

• Current Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Original Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Inventors: Fujimoto, Akira, Sasaki, Takashi, Asakawa, Koji, Ohashi, Kenichi
• Granted Patent: US 7,208,334 B2
• Time in Patent Office: Days
• US Class Current: 438/22
• CPC Class Codes: C08F 220/281 and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• CPC Class Codes: H01L 21/30608 Anisotropic liquid etching H01L21/3063 takes precedence
• CPC Class Codes: H01L 21/3081 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/67086 with the semiconductor substrates being dipped in baths or vessels
• CPC Class Codes: H01L 21/78 with subsequent division of the substrate into plural individual devices cutting to change the surface-physical characteristics or shape of semiconductor bodies H01L21/304
• CPC Class Codes: H01L 33/22 Roughened surfaces, e.g. at the interface between epitaxial layers

Abstract

Disclosed is an acid etching resistance material comprising a compound having a repeating unit represented by the following general formula (1):

• • (in the general formula (1), R¹ is a hydrogen atom or methyl group; R³ is a cyclic group selected from an alicyclic group and an aromatic group; R⁴ is a polar group; R² is a group represented by the following general formula (2); and j is 0 or 1):
  • (in the general formula (2), R⁵ is a hydrogen atom or methyl group).

Claims

1. A method of manufacturing a semiconductor device comprising a semiconductor substrate having a first electrode provided above the rear surface thereof and roughened side surfaces;

a light emitting layer formed above the semiconductor substrate; and

a second electrode provided above the light emitting layer or above the rear surface;

said method comprising;

forming a protective film above an entire surfaces of the semiconductor substrate including the first electrode, the light emitting layer and the second electrode, excluding the side surfaces, the protective film comprising an acid etching resistance material having a repeating unit represented by the following general formula (1);

(in the general formula (1), R¹ is a hydrogen atom or methyl group;

R³ is a cyclic group selected from an alicyclic group and an aromatic group;

R⁴ is a polar group;

R² is a group represented by the following general formula (2); and

j is 0 or 1;

(in the general formula (2), R⁵ is a hydrogen atom or methyl group);

treating the semiconductor substrate having the protective film formed thereof with an acidic etching solution; and

removing the protective film with an alkaline solution.

2. The method according to claim 1, wherein the acidic etching solution is a mixed solution comprising hydrochloric acid and aqueous hydrogen peroxide, and the method further comprising dicing the semiconductor substrate provided with the protecting film prior to treating the semiconductor substrate with the mixed solution.

3. The method according to claim 2, further comprising immersing the semiconductor substrate into concentrated hydrofluoric acid after treating the semiconductor substrate with the mixed solution comprising hydrochloric acid and aqueous hydrogen peroxide, thereby etching sidewalls of the semiconductor substrate to form a rugged surface.

4. The method according to claim 1, further comprising immersing the semiconductor substrate into concentrated hydrofluoric acid, thereby etching sidewalls of the semiconductor substrate to form a rugged surface.

5. The method according to claim 4, wherein the concentrated hydrofluoric acid contains hydrofluoric acid at a concentration of 25% or more.

6. The method according to claim 1, wherein the protecting film comprising a lower protecting film, and further comprising an upper protecting film on the lower protecting film.

7. The method according to claim 6, wherein the upper protecting film is formed of a novolac resin.

8. The method according to claim 1, wherein the semiconductor device is a light emitting element.

9. An acid etching resistance material comprising a compound having a repeating unit represented by the following general formula (1):

(in the general formula (1), R¹ is a hydrogen atom or methyl group;

R³ is a cyclic group selected from an alicyclic group and an aromatic group;

R⁴ is a polar group;

R² is a group represented by the following general formula (2); and

j is 0 or

     1);

(in the general formula (2), R⁵ is a hydrogen atom or methyl group).

10. The acid etching resistance material according to claim 9, wherein the cyclic group to be introduced as R³ into the general formula (1) is selected from the group consisting of adamantane, norbornane, cyclohexane and benzene ring.

11. The acid etching resistance material according to claim 9, wherein the polar group to be introduced as R⁴ into the general formula (1) is selected from the group consisting of carboxyl group, hydroxyl group and ketone.

12. The acid etching resistance material according to claim 9, further comprising not more than 50% by weight of hydrophobic low molecular compound.

13. The acid etching resistance material according to claim 12, wherein the hydrophobic low molecular compound is naphthoquinone diazide.

14. A copolymer comprising:

40 to 70 mol % of 3-hydroxy-1-methacryloyloxy-adamantane represented by the following chemical formula (A2); and

the balance of 2-acryloyloxypropyl phthalate represented by the following chemical formula (A4);

15. An acid etching resistance material comprising:

a resin having at least two kinds of repeating units represented by the following general formula (PS1); and

a photo acid generator which is capable of generating an acid as it is irradiated with light;

(in the general formula (PS1), R¹¹ and R¹³ are individually a hydrogen atom or methyl group;

R¹² is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one or two hydroxyl groups;

R¹⁴ is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one ketone groups; and

m and n represent individually a natural number).

16. The acid etching resistance material according to claim 15, wherein R¹¹ and R¹³ are individually a hydrogen atom, and R¹² is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having a single hydroxyl group.

17. The acid etching resistance material according to claim 16, wherein R¹² is adamantane having a single hydroxyl group, and R¹⁴ is adamantane having a single ketone group.

18. The acid etching resistance material according to claim 15, wherein the ratio of m:

n is confined within the range of 30;

70 to 70;

30.

19. A method of manufacturing a semiconductor device comprising:

forming a layer of a photosensitive etching resistance material on a substrate made of semiconductor or quartz glass, the photosensitive etching resistance material comprising an acid etching resistance material composed of a resin having at least two kinds of repeating units represented by the following general formula (PS1); and

a photo acid generator which is capable of generating an acid as it is irradiated with light;

(in the general formula (PS1), R¹¹ and R¹³ are individually a hydrogen atom or methyl group;

R¹² is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one or two hydroxyl groups;

R¹⁴ is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one ketone groups; and

m and n represent individually a natural number);

subjecting the substrate to patterning exposure;

heating the substrate;

subjecting the substrate to a developing treatment using an alkaline developing solution; and

subjecting the substrate to a fluoric acid etching treatment using a solution containing fluoric acid at a concentration ranging from 30% to 50%.

20. A method of manufacturing a semiconductor device comprising:

forming a sacrificial layer composed of quartz glass on a semiconductor substrate;

forming an element structure composed of semiconductor on the sacrificial layer;

forming a region composed of a material which is poor in hydrofluoric acid resistance on the semiconductor substrate;

covering the region composed of a material which is poor in hydrofluoric acid resistance with a photosensitive etching resistance material comprising an acid etching resistance material composed of a resin having at least two kinds of repeating units represented by the following general formula (PS1); and

a photo acid generator which is capable of generating an acid as it is irradiated with light;

(in the general formula (PS1), R¹¹ and R¹³ are individually a hydrogen atom or methyl group;

R¹² is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one or two hydroxyl groups;

R¹⁴ is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one ketone groups; and

m and n represent individually a natural number); and

removing the sacrificial layer by applying a hydrofluoric acid solution to the semiconductor substrate.

21. A method of manufacturing a semiconductor device comprising:

forming a region of a material which is excellent in hydrofluoric acid resistance on a semiconductor substrate;

forming a region of a material which is poor in hydrofluoric acid resistance over the region which is composed of a material which is excellent in hydrofluoric acid resistance;

covering the region which is poor in hydrofluoric acid resistance with a photosensitive etching resistance material comprising an acid etching resistance material composed of a resin having at least two kinds of repeating units represented by the following general formula (PS1); and

a photo acid generator which is capable of generating an acid as it is irradiated with light;

(in the general formula (PS1), R¹¹ and R¹³ are individually a hydrogen atom or methyl group;

R¹² is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one or two hydroxyl groups;

R¹⁴ is selected from the group consisting of adamantane, tricyclodecane, norbornane, isobornane, cyclohexane and cyclooctane, each having one ketone groups; and

m and n represent individually a natural number); and

subjecting the region which is composed of a material which is excellent in hydrofluoric acid resistance to an etching treatment using a solution of hydrofluoric acid.