Substrate processing method and substrate processing apparatus

1. A substrate processing method comprising: a processing liquid supplying step of supplying a processing liquid which has a solute and a solvent to a front surface of a substrate; a processing film forming step of solidifying or curing the processing liquid supplied to the front surface of the substrate to form on the front surface of the substrate a processing film which holds a removal object present on the front surface of the substrate; and a peeling step of supplying a peeling liquid to the front surface of the substrate to peel the processing film from the front surface of the substrate together with the removal object, wherein the peeling step includes a penetrating hole forming step of dissolving partially the processing film in the peeling liquid to form a penetrating hole on the processing film, wherein the solute of the processing liquid has a first component and a second component which is lower in solubility in the peeling liquid than the first component, the processing film forming step includes a step of forming the processing film which has a first solid formed by the first component and a second solid formed by the second component, and the penetrating hole forming step includes a step of dissolving the first solid by the peeling liquid to form the penetrating hole on the processing film.

2. The substrate processing method according to claim 1 , wherein the peeling step includes a peeling liquid entry step of entering the peeling liquid between the processing film and the front surface of the substrate via the penetrating hole.

3. The substrate processing method according to claim 1 , wherein the contained amount of the second component in the processing liquid is larger than the contained amount of the first component in the processing liquid.

4. The substrate processing method according to claim 1 , wherein the contained amount of the second component in the processing liquid is smaller than the contained amount of the first component in the processing liquid.

5. The substrate processing method according to claim 1 , wherein the solute further includes a third component higher in degree of solubility in the peeling liquid than the second component and lower in degree of solubility in the peeling liquid than the first component, and

the processing film forming step includes a step of forming the processing film which has a third solid formed by the third component at least at a portion adjacent to the front surface of the substrate.

6. The substrate processing method according to claim 1 , further comprising: a preprocessing liquid supplying step of supplying to the front surface of the substrate a preprocessing liquid which contains a solute having a third component higher in degree of solubility in the peeling liquid than the second component and lower in degree of solubility in the peeling liquid than the first component before supply of the processing liquid to the front surface of the substrate,

wherein the processing film forming step includes a step of forming the processing film which has a third solid formed by the third component at least at a portion adjacent to the front surface of the substrate.

7. The substrate processing method according to claim 1 , further comprising: a preprocessing liquid supplying step of supplying to the front surface of the substrate a preprocessing liquid which contains a solute having a third component higher in degree of solubility in the peeling liquid than the second component and lower in degree of solubility in the peeling liquid than the first component before supply of the processing liquid to the front surface of the substrate; and a preprocessing film forming step of solidifying or curing the preprocessing liquid before supply of the processing liquid to the front surface of the substrate to form a preprocessing film formed by the third component on the front surface of the substrate, wherein the peeling step includes a step of supplying the peeling liquid to the front surface of the substrate to peel the processing film and the preprocessing film from the front surface of the substrate together with the removal object.

8. The substrate processing method according to claim 1 , wherein the second component contains at least any one of novolac, polyhydroxystyrene, polystyrene, a polyacrylic acid derivative, a polymaleic acid derivative, polycarbonate, a polyvinyl alcohol derivative, a polmethacrylic acid derivative and a copolymer of a combination thereof.

9. The substrate processing method according to claim 1 , wherein the first component is a crack promoting component, and

the crack promoting component contains hydrocarbon and a hydroxy group and/or a carbonyl group.

10. The substrate processing method according to claim 1 , wherein the first component is expressed by at least any one of (B-1), (B-2) and (B-3) given below;

(B-1) is a compound which contains 1 to 6 of constituent units expressed by Chemical Formula 1 and in which each of the constituent units is bonded by a linking group L 1 ,

here, L 1 is selected at least from a single bond and any one of C 1˜6 alkylene, Cy 1 is a hydrocarbon ring of C 5˜30 , R 1 is each independently C 1˜5 alkyl, n b1 is 1, 2 or 3, and n b1′ is 0, 1, 2, 3 or 4;

(B-2) is a compound expressed by Chemical Formula 2,

here, R 21 , R 22 , R 23 and R 24 are each independently hydrogen or C 1˜5 alkyl, L 21 and L 22 are each independently C 1˜20 alkylene, C 1˜20 cycloalkylene, C 2˜4 alkenylene, C 2˜4 alkynylene or C 6˜20 arylene, these groups may be substituted by C 1˜5 alkyl or hydroxyl, and n b2 is 0, 1 or 2; and

(B-3) is a polymer which contains a constituent unit expressed by Chemical Formula 3 and has the weight average molecular weight (Mw) of 500 to 10,000,

R 25 is —H—CH 3 or —COOH.

11. The substrate processing method according to claim 1 , wherein the solubility of the second component in 5.0 mass % ammonia water is less than 100 ppm and the solubility of the first component in 5.0 mass % ammonia water is 100 ppm or more.

12. The substrate processing method according to claim 1 , wherein the mass of the second component is 0.1 to 50 mass %, as compared with an entire mass of the processing liquid.

13. The substrate processing method according to claim 1 , wherein the weight average molecular weight (Mw) of the second component is 150 to 500,000.

14. The substrate processing method according to claim 1 , wherein the first component and the second component are a synthetic resin.

15. The substrate processing method according to claim 1 , wherein the processing liquid supplying step includes a liquid film forming step of forming a liquid film of the processing liquid on the front surface of the substrate held horizontally, and

the method further comprises a film thinning step of rotating the substrate around a vertical axis passing through a central portion of the substrate to eliminate the processing liquid from the front surface of the substrate and to thin the liquid film.

16. The substrate processing method according to claim 1 , wherein the processing film forming step includes a step of forming the processing film in which the solvent remains in the interior of the processing film.

17. The substrate processing method according to claim 1 , wherein the processing film forming step includes a solvent evaporating step of evaporating the solvent from the processing liquid supplied to the front surface of the substrate.