阅读说明：本技术 抗蚀剂底层组合物和使用所述组合物形成图案的方法 (Resist underlayer composition and method for forming pattern using the same ) 是由 朴贤 崔有廷 权纯亨 裵信孝 白载烈 于 2020-02-25 设计创作，主要内容包括：本发明提供一种抗蚀剂底层组合物和一种使用抗蚀剂底层组合物来形成图案的方法,抗蚀剂底层组合物包含：聚合物,聚合物包含由化学式1表示的结构单元；和溶剂。化学式1的定义与详细描述中所描述的相同。[化学式1]<Image he="362" wi="700" file="DDA0002391668110000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides a resist underlayer composition and a method for forming a pattern using the same, the resist underlayer composition comprising: a polymer comprising a structural unit represented by chemical formula 1; and a solvent. The definition of chemical formula 1 is the same as described in the detailed description. [ chemical formula 1])

1. A resist underlayer composition comprising

A polymer comprising a structural unit represented by chemical formula 1; and

solvent:

[ chemical formula 1]

Wherein, in chemical formula 1,

L¹to L⁵Independently a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstitutedOr unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heterocycloalkylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or a combination thereof,

L⁶and L⁷Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, a single bond, a substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or a combination thereof,

R¹and R²Independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth) acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C1 to C30 thioalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, substituted or unsubstituted C6 to C30 thioaryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

n is one of integers of 1 to 1,000,

d is O, S, S (O)₂) C (O) or C (O) O,

m is an integer of 0 or 1,

is a connection point, and is a connection point,

A¹and A²Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, substituted or unsubstituted C3 to C10 cycloalkylene, substituted or unsubstitutedSubstituted C2 to C10 heterocycloalkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, or a combination thereof, and

A¹and A²Is a group represented by formula a:

[ chemical formula A ]

Wherein, in the chemical formula A,

L^ais a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or a combination thereof, and

is a connection point.

2. The resist underlayer composition of claim 1, wherein a¹And A²Independently, a substituted or unsubstituted C3 to C10 cycloalkylene, a substituted or unsubstituted C2 to C10 heterocycloalkylene, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, or a combination thereof.

3. The resist underlayer composition of claim 2, where A¹And A²Independently is a moiety selected from the group of moieties I:

[ group I ]

Wherein, in group I,

X¹to X¹⁵And X¹⁷To X²⁴Independently is N or CR^b，

X¹⁶Is NR^aOr CR^cR^d，

Z¹To Z⁶Independently O, S, C (O) or CR^cR^d，

R^a、R^b、R^c、R^d、R^e、R^f、R^gAnd R^hIndependently hydrogen, deuterium, hydroxyl, thiol, halogen, substituted or unsubstituted vinyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C10 alkoxy, or a combination thereof,

L^bis a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or a combination thereof, and

is a connection point.

4. The resist underlayer composition of claim 3, wherein A¹And A²Independently a moiety selected from the moieties of group I-1:

[ group I-1]

Wherein, in group I-1, is a point of attachment.

5. The resist underlayer composition of claim 1, wherein the polymer comprises at least one of structural units represented by chemical formulas 2 to 5:

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

Wherein, in chemical formulas 2 to 5,

R¹and R²Independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth) acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C1 to C30 thioalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, substituted or unsubstituted C6 to C30 thioaryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

n is one of integers of 1 to 1,000,

L⁶and L⁷Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstitutedSubstituted C6-C30 arylene, substituted or unsubstituted C1-C30 heteroalkylene, substituted or unsubstituted C3-C20 cycloalkylene, substituted or unsubstituted C2-C20 heterocycloalkylene, substituted or unsubstituted C1-C30 heteroalkenylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C2-C30 alkenylene, substituted or unsubstituted C2-C30 alkynylene, or combinations thereof,

L⁸to L²⁶Independently a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or combinations thereof, and

is a connection point.

6. The resist underlayer composition of claim 1, wherein the polymer comprises at least one of structural units represented by chemical formulas 6 to 8:

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

Wherein, in chemical formulas 6 to 8,

R¹and R²Independently isHydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth) acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C1 to C30 thioalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, substituted or unsubstituted C6 to C30 thioaryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

n is one of integers of 1 to 1,000,

L⁶and L⁷Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, a single bond, a substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or a combination thereof, and

is a connection point.

7. The resist underlayer composition of claim 1, wherein the weight average molecular weight of the polymer is in the range of 1,000 to 100,000.

8. The resist underlayer composition of claim 1, wherein the polymer is contained in an amount of 0.1 wt% to 50 wt% based on the total amount of the resist underlayer composition.

9. The resist underlayer composition of claim 1, wherein the resist underlayer composition further comprises at least one other polymer of an acrylic resin, an epoxy resin, a novolac resin, a glycoluril resin, and a melamine resin.

10. The resist underlayer composition of claim 1, wherein the resist underlayer composition further comprises at least one additive of a surfactant, a thermal acid generator, and a plasticizer.

11. A method of forming a pattern comprising

An etching object layer is formed on a substrate,

coating the resist underlayer composition as claimed in any one of claims 1 to 10 on the etching object layer to form a resist underlayer,

forming a photoresist pattern on the resist underlayer, an

The resist underlayer and the etching object layer are sequentially etched using the photoresist pattern as an etching mask.

12. The method of forming a pattern of claim 11, wherein the forming the photoresist pattern comprises

A photoresist layer is formed on the resist underlayer,

exposing the photoresist layer, and

developing the photoresist layer.

13. The method of forming a pattern according to claim 11, wherein the forming the resist underlayer further comprises heat-treating the coated resist underlayer composition at a temperature of 100 ℃ to 500 ℃.

Technical Field

The present invention relates to a resist underlayer composition and a method for forming a pattern using the same. In particular, the present invention relates to a photoresist underlayer composition formed between a semiconductor substrate and a photoresist layer, and a method of forming a photoresist pattern using the same.

Background

Recently, ultra-fine technology (ultra-fine technology) having a pattern with a size of several nanometers to several tens of nanometers has been developed in the semiconductor industry. Such hyperfine technology mainly requires an efficient photolithography (lithographic) technique.

The lithography technique includes: a method of forming a photoresist pattern on a semiconductor substrate such as a silicon wafer includes coating a photoresist layer on a semiconductor substrate such as a silicon wafer, exposing and developing the photoresist layer to form a thin layer, irradiating activating radiation such as Ultraviolet (UV) radiation while disposing a mask pattern having a pattern of devices, developing the resultant to obtain a photoresist pattern, etching the substrate using the photoresist pattern as a protective layer to form a fine pattern corresponding to the pattern on the surface of the substrate.

Since a technique for fabricating a hyperfine pattern is required, the photoresist is exposed using an activation radiation having a short wavelength (365 nm) such as i-line, a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), or the like. Therefore, research on solving the problem of the activation radiation generated due to the diffuse reflection from the semiconductor substrate, the standing wave, and the like has been conducted by interposing a resist underlayer having an optimal reflectance between the photoresist and the semiconductor substrate.

On the other hand, high-energy rays such as extreme ultraviolet (EUV; wavelength of 13.5 nm), E-beam (electron beam), and the like are used as a light source for manufacturing a fine pattern in addition to the activation radiation, and the light source does not have reflection from the substrate, but studies on improving the adhesion of the resist to the lower layer to improve the collapse of the pattern (collapse) have been widely conducted. In addition, in addition to reducing problems caused by light sources, research on improving etch selectivity and chemical resistance of a resist underlayer is also widely conducted.

Disclosure of Invention

Embodiments provide a resist underlayer composition that optimizes reflectivity for a predetermined wavelength while improving coating characteristics, adhesion to photoresist, and a fast etching rate.

Another embodiment provides a method of forming a pattern using the resist underlayer composition.

According to an embodiment, a resist underlayer composition comprises: a polymer comprising a structural unit represented by chemical formula 1; and a solvent.

[ chemical formula 1]

In the chemical formula 1, the first and second,

L¹to L⁵Independently a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or combinations thereof,

L⁶and L⁷Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, a single bond, a substituted or unsubstituted C1 to C30 alkylene, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C1 to C30 heteroalkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C2 to C20 heterocycloalkylene, a substituted or unsubstituted C1 to C30 heteroalkenylene, a substituted or unsubstituted C2 to C30 heteroarylene, a substituted or unsubstituted C2 to C30 alkenylene, a substituted or unsubstituted C6342 alkenyleneSubstituted C2 to C30 alkynylene groups or combinations thereof,

R¹and R²Independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth) acrylate, oxetanyl (oxyethane group), thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C1 to C30 thioalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, substituted or unsubstituted C6 to C30 thioaryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

n is one of integers of 1 to 1,000,

d is O, S, S (O)₂) C (O) or C (O) O,

m is an integer of 0 or 1,

is a connection point, and is a connection point,

A¹and A²Independently O, S, S (O), S (O)₂) C (O), C (O) O, OC (O) O, substituted or unsubstituted C3 to C10 cycloalkylene, substituted or unsubstituted C2 to C10 heterocycloalkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, or combinations thereof, and

A¹and A²Is a group represented by formula a:

[ chemical formula A ]

Wherein, in the chemical formula A,

L^ais a single bond, substituted or unsubstituted C1 to C30 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C30 heteroalkylene, substituted or unsubstitutedC3 to C20 cycloalkylene, substituted or unsubstituted C2 to C20 heterocycloalkylene, substituted or unsubstituted C1 to C30 heteroalkenylene, substituted or unsubstituted C2 to C30 heteroarylene, substituted or unsubstituted C2 to C30 alkenylene, substituted or unsubstituted C2 to C30 alkynylene, or combinations thereof, and

is a connection point.

According to another embodiment, a method of forming a pattern includes forming an etching object layer (etchingsubject layer) on a substrate, coating the aforementioned resist underlayer composition on the etching object layer to form a resist underlayer, forming a photoresist pattern on the resist underlayer, and sequentially etching the resist underlayer and the etching object layer using the photoresist pattern as an etching mask.

The resist underlayer composition can have improved coating characteristics, adhesion to photoresist, and fast etch rate.