• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:NL2001346A1
    申请号:NL2001346
    申请日:2008-03-03
    公开日:2008-04-22
    发明作者:Ching-Yu Chang
    申请人:Taiwan Semiconductor Mfg；
    IPC主号:
    专利说明:

    Title: Watermark defect prevention for immersion lithography
    Background
    As semiconductor manufacturing technologies continuously advance to smaller object dimensions such as 65 nanometers, 45 nanometers and less, immersion lithography processes become. Immersion lithography processes, however, cause a residue of water droplets after an exposure process. Such a water drop residue can cause watermark defects and thereby degrade semiconductor fabrication or even cause errors during semiconductor fabrication.
    An improved immersion lithography system is needed in which the damage caused by watermark defects is prevented and / or reduced.
    Brief description of the figures
    Aspects of the present explanation are best understood on the basis of the following detailed description read with the accompanying figures. It is noted that, in accordance with standard usage in the industry, several parts are not drawn to scale. The dimensions of the various parts may be increased or reduced as desired for clarity of description.
    FIG. 1 shows a cross section of an example of a semiconductor device 100 with a photosensitive layer that is exposed during an immersion lithography process.
    FIG. 2 and 3 show cross-sections of an example of a semiconductor device with a photosensitive layer and a watermark formed thereon during immersion lithography processes.
    FIG. 4 shows a schematic view of a photosensitive layer with chemically bonded quenchers.
    FIG. 5a-5c show schematic views of various embodiments of a photosensitive layer with a polymer and chemical quenchers bound to the polymer.
    FIG. 6 shows a schematic view of a photosensitive layer with physically captured quenchers.
    FIG. 7a-7j show schematic views of various embodiments of a photosensitive layer with quenchers with reduced mobility.
    FIG. 8a-8b show schematic views of various embodiments of a photosensitive layer with hydrophobic quenchers.
    FIG. 9 is a flow chart of an embodiment of an immersion photolithography pattern fabrication method
    Detailed description
    It will be appreciated that the following disclosure provides many different embodiments, or examples, for implementing various measures of various embodiments. Specific examples of components and devices are described below to simplify the current explanation. These are, of course, only examples and are not intended to be limiting. For example, forming a first structure on top of or on a second structure in the following description may include embodiments in which the first and second structure are formed in direct contact, and may also include embodiments in which additional structures may be formed between the first and second structures such that the first and second structures are not in direct contact. Additionally, the current explanation may repeat reference numerals and / or letters in the various examples. This repetition serves for simplicity and clarity and does not in itself represent a relationship between the various embodiments and / or configurations.
    FIG. 1 provides a cross-sectional view of a semiconductor device 100 during immersion lithography exposure process. The semiconductor device 100 can be a semiconductor weaver or other suitable device. In the present embodiment, the semiconductor device 100 comprises a silicon substrate 110 with organic soil antireflection coating (BARC), inorganic soil antireflection layer, etching resistance organic layer, adhesion enhancing organic layer, various doped regions, dielectric structures, and multi-level connections. The substrate may alternatively comprise other suitable semiconductor materials, including Ge, SiGe or GaAs. The substrate may alternatively comprise a non-semiconductor material such as a glass plate for thin film transistor liquid crystal display devices (TFT-LCD). The semiconductor device 100 may further comprise one or more layers of material in which patterns are to be applied.
    The semiconductor device 100 comprises a photosensitive layer (photoresist or resist) 120. In the present embodiment, the resist layer 120 has a thickness between about 50 Angstroms and 5000 Angstroms.
    In another embodiment, the resist layer 120 may have a thickness between about 500 Angstroms and 2000 Angstroms. The resist layer 120 uses a chemical reinforcement (CA) resist material. The resist layer 120 comprises a polymeric material that becomes soluble in a developer such as a basic solution when the polymer reacts with acid. The resist 120 further comprises a solvent filling in the polymer. The solvent may be partially evaporated due to an earlier baking process. The resist 120 also includes a photo acid generator (PAG) 130 material, with PAG molecules distributed in the solvent and / or polymer. When it absorbs photo energy, the PAG 130 disintegrates and forms a small amount of acid. The PAG 130 can have a concentration between about 1 and 15 weight percent of the resist polymer 120.
    Further in the present embodiment, the resist 120 also comprises a quencher material 140 that divides into the solvent and polymer. The quencher 140 is a basic type and is capable of neutralizing acid. Collectively or alternatively, the quencher can inhibit other active components of the resist 120, such as preventing PAG and photoacid from reacting. The quencher 140 can have a concentration between 0.5 and 8 weight percent of the resist. The quencher 140 may alternatively have a concentration of about% of the concentration of the PAG 130 by weight for the exposure process. In one example, the quencher 140 comprises a nitrogen atom with an unpaired electron capable of neutralizing an acid. In an exposure process step during an immersion photolithographic patterning, the resist layer 120 is exposed to a radiant energy such as deep ultraviolet (DUV) through a photomask (mask or reticle) with a predetermined pattern, resulting in a resist pattern comprising a plurality of unexposed areas such as unexposed structures 120a and a plurality of exposed areas such as exposed structures 120b. The radiant energy can include a 248 nanometer beam from Krypton Fluoride (KrF) excimer lasers or a 193 nanometer beam from Argon Fluoride (ArF) excimer lasers. The immersion lithography further comprises an immersion fluid between the semiconductor device 100 and a lens of a lithography system that is used to perform the exposure process step. The immersion fluid can comprise deionized water (D1 water or DIW). The fluid may further comprise chemical additives such as acid, salt or polymer. The fluid may alternatively comprise other suitable fluids with a refractive index higher than 1.44, the refractive index of DIW. During an exposure process, the water drop residue, such as an exemplary water drop 150, can be left on the resist layer after the exposure process.
    In previous immersion lithography patterning processes, the water drop residue may cause problems such as forming a watermark as illustrated in cross sections of a semiconductor device 200 of FIG. 2 and 3. A water droplet 130 remaining on a photosensitive layer 120 of the semiconductor device 200 can provide a path for PAG 130 and quencher 140. The quencher 140 can diffuse into unexposed resist region 120a in the water droplet and further diffuse into the exposed resist region 120 wherein the photogenerated acid is neutralized and / or exposure efficiency in the exposed areas is reduced. Furthermore, the exposed PAG falls apart as PAG anion and acid, which is more soluble in water than unexposed PAG. The photogenerated acid can diffuse into the water droplet with additional effects so that the exposed areas of the resist 120 have reduced photogenerated acid. Thus, these exposed areas of the resist layer 120 may have insufficient photogenerated acid to induce a cascade of chemical transformation (acid enhancement) after the exposure process step, and / or may not be completely soluble in development solution at a development process step. Thus, an unexpected T-top resist structure (bridge profile or watermark) 120c can be formed on the exposed areas of the resist layer 120 in which the top resist material of the exposed area is not soluble in a developing solution.
    According to the present explanation, the quencher 140 has reduced mobility so that the diffusion through the water droplet is substantially reduced. In one example, the mobility of the quencher is reduced such that the quencher is capable of being leached to less than about 10 13 moles per cm 2 in an immersion fluid during immersion lithography.
    In an embodiment as shown in FIG. 4, the quencher 140 is chemically bonded to a polymer 160 so that the quencher has reduced mobility. The polymer 160 becomes soluble in a developing solution after reaction with an acid. The polymer 160 further comprises a short chain polymer, which is soluble in developing solution. The quencher 140 is unable to diffuse into the water droplet, resulting in a limited range of mobility due to chain movements of the polymer 160 and / or quencher 140.
    With reference to FIG. 5a, the quencher 140 may be bonded to a carbon unit 162 of the polymer 160 by a nitrogen atom 142 of the quencher. In the present embodiment, the nitrogen atom 142 comprises an unpaired electron to neutralize acid or other active components of the resist. The quencher 140 includes first and second chemical groups 144, 146 such as alkyl groups attached to the nitrogen atom 142. An alkyl group can include H, CH 3, C 2 H 5, CF 3, C 2 F 5, ring-type polymer or ring-type polymer with the end of the ring bonded to nitrogen atom 142. The first and second chemical groups 144 and 146 may alternatively comprise other chemical groups. In other examples, the polymer 160 may have two carbon units 164 in FIG. 5b, or 3 carbon units 166 in FIG. 5c, or even more carbon units bound to the nitrogen 142 of the quencher. Such a carbon structure has multiple carbon units in a chain and provides some flexibility to the bound quencher 140. The polymer alternatively includes other atomic units bound to the quencher 140.
    With reference to FIG. 6, in another embodiment, the quencher 140 may be physically trapped (completely or partially) in the polymer 160. The quencher 140 may have a size that is substantially large relative to an average grid size of the network of the polymer 160 such that the quencher 140 is physically caught inside. The quencher 140 may alternatively have a certain structural group to improve physical entanglement. For example, the quencher 140 may include a long tail (a long chain) or a branched chain so that the quencher 140 may be physically entangled with or trapped by the polymer 160. In another embodiment, the quencher 140 may include a ring structure, a long chain, a branched group, or combinations thereof to reduce quench mobility.
    FIG. 7a-7j show various exemplary structures of the quencher. In the quencher in FIG. 7a includes two alkyl groups and a ring structure such as a carbon ring. A quencher in FIG. 7d includes one alkyl group and two ring structures. A quencher in FIG. 7b comprises three ring structures. A quencher in FIG. 7c comprises two alkyl groups and one ring structure with an oxygen atom. A quencher in FIG. 7e includes two alkyl groups and a long tail such as a carbon chain. A quencher in FIG. 7f comprises two alkyl groups and a long tail with an oxygen atom. A quencher in FIG. 7g comprises one ring structure with an oxygen and two long chain structures. A quencher in FIG. 7h includes two alkyl groups and one branched structure with two short tails. A quencher in FIG. 7i comprises two alkyl groups and one branched structure with two long tails. A quencher in FIG. 7j comprises two alkyl groups and one branched structure with three short tails. Other combinations can be implemented to adjust the mobility of the quencher for optimum performance.
    With reference to FIG. 8a and 8b, in another example, the quencher is hydrophobic and therefore difficult to diffuse into a drop of water. The quencher can comprise at least one hydrophobic group. The quencher comprises, for example, a fluoride. The quencher in FIG. 8a comprises three alkyl groups and at least one of them has a fluoride. The quencher in FIG. 8b includes an alkyl group, one ring with an oxygen, and a long chain with multiple fluoride.
    In another embodiment, water droplets remaining on the resist layer can be treated with acid immediately after the exposure process. The acid treatment can be implemented by spraying acid on the resist surface (and / or the water droplets thereon) through a chemical inlet integrated into the immersion lithography system. The pH value of the treated water droplets can be adjusted to a value below about 6. Thus, the quencher has a reduced diffusion rate in the water droplet. Furthermore, photogenerated acid can also have a reduced diffusion rate in the water drop. The acid treatment can also diffuse into the resist film and essentially compensate for the leaching of the photo acid.
    In various embodiments, the mobility from the quencher to the drop of water on the resist layer is substantially reduced. The watermark effect is also substantially reduced. Various embodiments can be adapted or combined for an optimized resist patterning process.
    With reference to FIG. 9 a flowchart of an immersion lithography method 900 forms a resist pattern as described. The method 900 includes a step 902 for forming a photosensitive (resist) layer on a semiconductor weaver. The resist layer is substantially the same as the resist layer 120 of FIG. 1, wherein the quenching material has reduced mobility. The quencher may have structures similar to those shown in FIG. 5a-5c, FIG. 7a-7j and FIG. 8a-8b, or combinations thereof.
    The method 900 further comprises a step 904 for illuminating the resist layer with a radiant energy such as DUV through a photomask and an immersion fluid. The immersion fluid can be DIW or other suitable fluids with a high refractive index and is placed between the semiconductor weaver and lens of an immersion lithography system for implementing the method 900. Since the quencher has reduced mobility, the quencher has a reduced leaching in water droplets left behind on the resist layer after the exposure step 904.
    The method 900 then proceeds to a step 906 for baking (baking after exposure or PEB) of the resist layer. The baking temperature can be between approximately 80 ° C and 150 ° C. The baking can have a duration of for example a few minutes. The baking step may further comprise removing water droplets remaining on the resist layer. The method 900 then proceeds to a step 908 for developing the resist layer in a developing solution. The exposed resist areas are essentially resolved.
    The method 900 may further include a step between the exposure step and the baking step 906 for treating the water droplets remaining on the resist layer so that the water droplets have a pH value below 6. Such acid-treated water droplets can also neutralize the diffusion from the basic quencher to the water drop. This can reduce the influence of the diffusion of the quencher to the exposed resist areas through the water droplets and can also reduce the diffusion of the acid from the exposed resist areas into the water droplets.
    Thus, the present disclosure provides a photoresist material with a polymer that becomes soluble in a basic solution in response to reaction with acid. The material includes a photo acid generator (PAG) that disintegrates to form acid in response to radiant energy and a quencher that is able to neutralize acid and has reduced mobility.
    In some embodiments, the quencher comprises a concentration of more than about half a weight percent of the polymer. The quencher may be capable of being leached to an amount of less than about 5 x 10 13 mol / cm 2 in an immersion fluid. The immersion fluid can comprise water. The immersion fluid can comprise a suitable fluid with a refractive index (s) greater than 1.44. The quencher can be chemically bonded to the polymer. The polymer can comprise at least one carbon unit that is bound to the quencher. The at least one carbon unit can be bound to a nitrogen atom of the quencher. The quencher can include a nitrogen atom with an unpaired electron. The quencher can comprise at least one ring structure connected to the nitrogen atom. The quencher can comprise at least one four-carbon chain connected to the nitrogen atom. The quencher can comprise at least four atomic units connected to the nitrogen atom of the quencher. The quencher can comprise at least one branch chain connected to the nitrogen atom of the quencher. The quencher can be substantially hydrophobic. The quencher can include fluoride.
    The present disclosure also provides a material with a polymer that becomes soluble in a basic solution in response to reaction with acid. The material comprises a plurality of photo acid generators (PAGs) that disintegrate to form acid in response to radiant energy; and a plurality of quenchers capable of neutralizing acid and having reduced mobility by at least: being chemically bonded to the polymer; - be substantially hydrophobic; and / or - be physically trapped in the polymer.
    In some embodiments, the plurality of quenchers comprises a concentration of about 1A of a concentration of the plurality of PAGs. Each of the plurality of quenchers can include a nitrogen atom with an unpaired electron. Each of the plurality of quenchers may comprise a chemical group attached to the nitrogen, the chemical group being selected from the group consisting of one alkyl group, a ring structure, a long chain, a branched group, and combinations thereof. The plurality of quenchers may include reduced mobility such that the plurality of quenchers is capable of being leached less than about 5 x 10 13 moles per cm 2 in an immersion fluid. The material may further comprise a solvent in the polymer.
    The present explanation also provides a method for immersion lithography. The method comprises forming a photosensitive layer on a substrate, the photosensitive layer comprising; a polymer that becomes soluble in a basic solution in response to reaction with acid; a plurality of photo acid generators (PAGs) that disintegrate to form acid in response radiant energy; and a plurality of quenchers capable of neutralizing acid and having reduced mobility. The method comprises exposing the photosensitive layer using an immersion lens system; baking the photosensitive layer wherein the photosensitive layer is capable of leaching out the plurality of quenchers less than about 5 x 10 13 moles per cm 2 in an immersion fluid; and developing the photosensitive layer. The method may further comprise an acid treatment such that the pH value of water droplets on the photosensitive layer is lower than 6 after exposure of the photosensitive layer. In the method, baking the photosensitive may include removing water drop.
    The foregoing has set forth measures of various embodiments so that one skilled in the art can better understand the detailed description. Those skilled in the art will understand that the current disclosure can be used as a basis for designing or adapting other processes and structures to perform the same goals and / or achieve the same benefits of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not deviate from the spirit and scope of the present disclosure as set forth in the following claims, and that various changes of substitutions and changes can be made thereto without departing from the spirit and scope of the current explanation as described in the following claims.
    权利要求:
    Claims (23)
    [1]
    A material for use in immersion lithography, comprising: a polymer that becomes soluble in a basic solution in response to reaction with acid; a photo acid generator (PAG) that disintegrates to form an acid in response to a radiant energy; and a quencher capable of neutralizing acid and having reduced mobility.
    [2]
    The material of claim 1, wherein the quencher comprises a concentration of more than about 0.5 weight percent of the polymer, for example, more than 0.5 weight percent.
    [3]
    The material of claim 1, wherein the quencher is capable of being leached to an amount of less than about 5 x 10 13 mol / cm 2 in a fluid used in immersion lithography, e.g., less than 5 x 10 13 mol / cm 2.
    [4]
    The material of claim 3, wherein the fluid comprises water.
    [5]
    The material of claim 3, wherein the fluid comprises a refractive index (s) of greater than 1.44.
    [6]
    The material of claim 1, wherein the quencher is chemically bonded to the polymer.
    [7]
    The material of claim 6, wherein the polymer comprises at least one carbon unit bonded to the quencher.
    [8]
    The material of claim 7, wherein the at least one carbon unit is bonded to a nitrogen atom of the quencher.
    [9]
    The material of claim 1, wherein the quencher comprises a nitrogen atom with an unpaired electron.
    [10]
    The material of claim 9, wherein the quencher comprises at least one ring structure associated with the nitrogen atom.
    [11]
    The material of claim 9, wherein the quencher comprises at least four atomic units connected to the quencher nitrogen atom.
    [12]
    The material of claim 9, wherein the quencher comprises at least one branch chain connected to the quencher nitrogen atom.
    [13]
    The material of claim 1, wherein the quencher is substantially hydrophobic.
    [14]
    The material of claim 13, wherein the quencher comprises fluoride.
    [15]
    A material comprising: a polymer that becomes soluble in a basic solution in response to reaction with acid; a plurality of photo acid generators (PAGs) that disintegrate to form acid in response to a radiant energy; and a plurality of quenchers capable of neutralizing acid and having reduced mobility by being at least one of: chemically bonded to the polymer; to be substantially hydrophobic; and physically trapped in the polymer.
    [16]
    The material of claim 15, wherein the plurality of quenchers comprises a concentration of about one-fourth of a concentration of the plurality of PAGs, for example, a fourth.
    [17]
    The material of claim 15, wherein one or more of the plurality of quenchers comprises a nitrogen atom with an unpaired electron.
    [18]
    The material of claim 17, wherein each of the plurality of quenchers comprises a chemical bonded to the nitrogen, wherein the chemical group is selected from the group consisting of an alkyl group, a ring structure, a long chain, a branched group, and combinations thereof.
    [19]
    The material of claim 15, wherein the plurality of quenchers is configured to have reduced mobility such that the quechers are capable of being leached to an amount of less than about 5 x 10 13 mol / cm 2 in an immersion fluid, e.g., less than 5 x 10 * 13 mol / cm 2.
    [20]
    The material of claim 15, further comprising a solvent in the polymer.
    [21]
    A method for immersion lithography, comprising: forming a photosensitive layer on a substrate, the photosensitive layer comprising: a polymer that becomes soluble in a basic solution in response to reaction with acid; a plurality of photo acid generators (PAGs) that disintegrate to form acid in response to a radiant energy; and a plurality of quenchers capable of neutralizing acid and having reduced mobility; exposing the photosensitive layer in an immersion lithography system with an immersion fluid; baking the photosensitive layer, wherein the photosensitive layer is capable of leaching out the plurality of quenchers at a rate of less than about 5 x 10 13 mol / cm 2 in the immersion fluid; and developing the exposed photosensitive layer.
    [22]
    The method of claim 21, further comprising performing an acid treatment such that a pH value of water droplets on the photosensitive layer is lower than 6 after exposing the photosensitive layer.
    [23]
    The method of claim 21, wherein baking the photosensitive layer is configured to simplify the removal of water droplets.
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    法律状态:
    2008-07-01| AD1A| A request for search or an international type search has been filed|
    2009-06-02| RD2N| Patents in respect of which a decision has been taken or a report has been made (novelty report)|Effective date: 20090409 Effective date: 20090401 |
    优先权:
    申请号 | 申请日 | 专利标题
    US72264605P| true| 2005-09-30|2005-09-30|
    US72264605|2005-09-30|
    US27163905|2005-11-10|
    US11/271,639|US7927779B2|2005-06-30|2005-11-10|Water mark defect prevention for immersion lithography|NL2002950A| NL2002950C2|2005-09-30|2009-06-02|WATER BRAND DEFECTIVE PREVENTION FOR IMMERSION LITHOGRAPHY.|
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