The present invention relates to systems and methods for substrate processing, and more particularly to a method and system for defectivity metrology during Directed Self Assembly (DSA) patterning.
The need to remain competitive in cost and performance in the production of semiconductor devices has caused a continuous increase in device density of integrated circuits. Higher integration and miniaturization in a semiconductor integrated circuit, requires an associated miniaturization of a circuit pattern formed on a semiconductor wafer.
Photolithography is a standard technique used to manufacture semiconductor integrated circuitry by transferring geometric shapes and patterns on a mask to the surface of a semiconductor wafer. Current state-of-the-art photolithography tools only allow feature sizes down to about 25 nm. Accordingly, new methods are needed to provide smaller features.
Directed Self Assembly (DSA) of integrated circuits has been used to further reduce feature sizes. One type of DSA includes self-assembly of block copolymers (BCPs), which has been considered a potential tool for improving the resolution to better values than those obtainable by prior art lithography methods alone. Block copolymers are useful compounds in nanofabrication, because they may undergo an order-disorder transition on cooling below a certain temperature (order-disorder transition temperature TOD), resulting in phase separation of copolymer blocks of different chemical nature to form ordered, chemically distinct domains with dimensions of tens of nanometers or even less than 10 nm. The size and shape of the domains may be controlled by manipulating the molecular weight and composition of the different block types of the copolymer. The interfaces between the domains may have widths of the order of 1 nm to 5 nm and may be manipulated by modification of the chemical compositions of the blocks of the copolymer.
A block copolymer may form many different phases upon self-assembly, dependent upon the volume fractions of the blocks, degree of polymerization within each block type (i.e., number of monomers of each respective type within each respective block), the optional use of a solvent and surface interactions. When applied in a thin film, the geometric confinement may present additional boundary conditions, which may limit the number of phases. In general, spherical (e.g., cubic), cylindrical (e.g., tetragonal or hexagonal) and lamellar phases (i.e., self-assembled phases with cubic, hexagonal or lamellar space-filling symmetry) are practically observed in thin films of self-assembled block copolymers, and the phase type observed may depend upon the relative volume fractions of the different polymer blocks. The self-assembled polymer phases may orient with symmetry axes parallel or perpendicular to the substrate and lamellar and cylindrical phases are interesting for lithography applications, because they may form line and spacer patterns and contact hole arrays, respectively, and may provide good contrast when one of the domain types is subsequently etched.
Two methods used to guide DSA of a block copolymer onto a surface are grapho-epitaxy and chemical pre-patterning, also called chemi-epitaxy. In the grapho-epitaxy method, self-organization of a block copolymer is guided by topological pre-patterning of the substrate. A self-aligned block copolymer can form a parallel linear pattern with adjacent lines of the different polymer block domains in the trenches defined by the patterned substrate. For example, if the block copolymer is a di-block copolymer with A and B blocks within the polymer chain, where A is hydrophilic and B is hydrophobic in nature, the A blocks may assemble into domains formed adjacent to a side-wall of a trench if the side-wall is also hydrophilic in nature. Resolution may be improved over the resolution of the patterned substrate by the block copolymer pattern subdividing the spacing of a pre-pattern on the substrate.
Accordingly, to achieve the advantages provided by grapho-epitaxy and chemi-epitaxy of block copolymers, new lithographic patterning and DSA techniques are required, including the ability to integrate such materials in patterning workflows. One example of a block copolymer is polystyrene-b-poly(methyl methacrylate) (PMMA). However, when removing the PMMA portion from the polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) layer to leave behind a polystyrene (PS) pattern, conventional etching techniques have suffered. Due to the organic nature of both materials, and their similarities, developing an etch chemistry with suitable etch selectivity has been challenging. Furthermore, conventional etch processes produce pattern defectivity, such as line edge roughness/line width roughness (LER/LWR), that are unacceptable as per the semiconductor device performance requirements. In extreme cases, the defectivity of the PS can be catastrophic due to pattern collapse. For these reasons, defect detection methods are needed.
A further challenge lies in detecting defects which are sub-surface and in the bulk of phase separated BCP films. Commonly used metrology methods like Critical Dimension Scanning Electron Microscope (CDSEM) and optical scattering methods cannot detect such defects because of low selectivity etching processes, which tend to mitigate prior to detection.
Provided is a method for defectivity metrology during DSA patterning. In an embodiment, a method may include providing the substrate in a process chamber of the fabrication system, the substrate comprising a top layer with a first material and a second material and an underlying layer. The method may also include performing a vacuum ultra-violet (VUV) curing process on the substrate to enhance etch resistance of the second material during a subsequent etch process and to enable metrology to detect defects underneath a surface of the top layer. Additionally, the method may include performing a metrology process to quantify defects made visible by the VUV curing process, the metrology process generating a defect profile of the top layer. Further, the method may include performing an etch process to remove the second material using a dry plasma process and utilizing the defect profile, the etch process generating a first pattern on the substrate. Additionally, the method may include controlling one more integration variables in order to meet target integration objectives during one or more process including the VUV curing process, the metrology process, and/or the etch process.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the general description of the invention given above, and the detailed description given below, serve to describe the invention.
Methods and systems for patterning sidewall shapes are presented. However, one skilled in the relevant art will recognize that the various embodiments may be practiced without one or more of the specific details, or with other replacement and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of various embodiments of the invention.
Similarly, for purposes of explanation, specific numbers, materials, and configurations are set forth in order to provide a thorough understanding of the invention. Nevertheless, the invention may be practiced without specific details. Furthermore, it is understood that the various embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale. In referencing the figures, like numerals refer to like parts throughout.
Reference throughout this specification to “one embodiment” or “an embodiment” or variation thereof means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention, but does not denote that they are present in every embodiment. Thus, the appearances of the phrases such as “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. Various additional layers and/or structures may be included and/or described features may be omitted in other embodiments.
Additionally, it is to be understood that “a” or “an” may mean “one or more” unless explicitly stated otherwise.
Various operations will be described as multiple discrete operations in turn, in a manner that is most helpful in understanding the invention. However, the order of description should not be construed as to imply that these operations are necessarily order dependent. In particular, these operations need not be performed in the order of presentation. Operations described may be performed in a different order than the described embodiment. Various additional operations may be performed and/or described operations may be omitted in additional embodiments.
As used herein, the term “substrate” means and includes a base material or construction upon which materials are formed. It will be appreciated that the substrate may include a single material, a plurality of layers of different materials, a layer or layers having regions of different materials or different structures in them, etc. These materials may include semiconductors, insulators, conductors, or combinations thereof. For example, the substrate may be a semiconductor substrate, a base semiconductor layer on a supporting structure, a metal electrode or a semiconductor substrate having one or more layers, structures or regions formed thereon. The substrate may be a conventional silicon substrate or other bulk substrate comprising a layer of semi-conductive material. As used herein, the term “bulk substrate” means and includes not only silicon wafers, but also silicon-on-insulator (“SOI”) substrates, such as silicon-on-sapphire (“SOS”) substrates and silicon-on-glass (“SOG”) substrates, epitaxial layers of silicon on a base semiconductor foundation, and other semiconductor or optoelectronic materials, such as silicon-germanium, germanium, gallium arsenide, gallium nitride, and indium phosphide. The substrate may be doped or undoped.
As used herein, the term “radiation sensitive material” means and includes photosensitive materials such as photoresists.
As used herein, the term “polymer block” means and includes a grouping of multiple monomer units of a single type (i.e., a homopolymer block) or multiple types (i.e., a copolymer block) of constitutional units into a continuous polymer chain of some length that forms part of a larger polymer of an even greater length and exhibits a XN value, with other polymer blocks of unlike monomer types, that is sufficient for phase separation to occur. X is the Flory-Huggins interaction parameter and N is the total degree of polymerization for the block copolymer. According to embodiments of the present invention, the XN value of one polymer block with at least one other polymer block in the larger copolymer may be equal to or greater than about 10.5.
As used herein, the term “block copolymer” means and includes a polymer composed of chains where each chain contains two or more polymer blocks as defined above and at least two of the blocks are of sufficient segregation strength (e.g., XN>10.5) for those blocks to phase separate. A wide variety of block polymers are contemplated herein including di-block copolymers (i.e., polymers including two polymer blocks (AB)), tri-block copolymers (i.e., polymers including three polymer blocks (ABA or ABC)), multi-block copolymers (i.e., polymers including more than three polymer blocks (ABCD, etc.)), and combinations thereof.
The terms “microphase segregation” and “microphase separation,” as used herein mean and include the properties by which homogeneous blocks of a block copolymer aggregate mutually, and heterogeneous blocks separate into distinct domains. In the bulk, block copolymers can self-assemble into ordered morphologies, having spherical, cylindrical, and lamellar, bicontinuous gyroid, or miktoarm star micro domains, where the molecular weight of the block copolymer dictates the sizes of the micro domains formed.
The domain size or pitch period (Lo) of the self-assembled block copolymer morphology may be used as a basis for designing critical dimensions of the patterned structure. Similarly, the structure period (Ls), which is the dimension of the feature remaining after selectively etching away one of the polymer blocks of the block copolymer, may be used as a basis for designing critical dimensions of the patterned structure. The lengths of each of the polymer blocks making up the block copolymer may be an intrinsic limit to the sizes of domains formed by the polymer blocks of those block copolymers. For example, each of the polymer blocks may be chosen with a length that facilitates self-assembly into a desired pattern of domains, and shorter and/or longer copolymers may not self-assemble as desired.
The term “annealing” or “anneal” as used herein means and includes treatment of the block copolymer so as to enable sufficient microphase segregation between the two or more different polymeric block components of the block copolymer to form an ordered pattern defined by repeating structural units formed from the polymer blocks. Annealing of the block copolymer in the present invention may be achieved by various methods known in the art, including, but not limited to: thermal annealing (either in a vacuum or in an inert atmosphere, such as nitrogen or argon), solvent vapor-assisted annealing (either at or above room temperature), supercritical fluid-assisted annealing, or absorption-based annealing (e.g., optical baking). As a specific example, thermal annealing of the block copolymer may be conducted by exposing the block copolymer to an elevated temperature that is above the glass transition temperature (Tg), but below the degradation temperature (Td) of the block copolymer, as described in greater detail hereinafter. Other conventional annealing methods not described herein may also be utilized.
The ability of block copolymers to self-organize may be used to form mask patterns. Block copolymers are formed of two or more chemically distinct blocks. For example, each block may be formed of a different monomer. The blocks are immiscible or thermodynamically incompatible, e.g., one block may be polar and the other may be non-polar. Due to thermodynamic effects, the copolymers will self-organize in solution to minimize the energy of the system as a whole; typically, this causes the copolymers to move relative to one another, e.g., so that identical blocks aggregate together, thereby forming alternating regions containing each block type or species. For example, if the copolymers are formed of polar (e.g., organometallic containing polymers) and non-polar blocks (e.g., hydrocarbon polymers), the blocks will segregate so that non-polar blocks aggregate with other non-polar blocks and polar blocks aggregate with other polar blocks. It will be appreciated that the block copolymers may be described as a self-assembling material since the blocks can move to form a pattern without active application of an external force to direct the movement of particular individual molecules, although heat may be applied to increase the rate of movement of the population of molecules as a whole.
In addition to interactions between the polymer block species, the self-assembly of block copolymers can be influenced by topographical features, such as steps or guides extending perpendicularly from the horizontal surface on which the block copolymers are deposited. For example, a di-block copolymer, a copolymer formed of two different polymer block species, may form alternating domains, or regions, which are each formed of a substantially different polymer block species. When self-assembly of polymer block species occurs in the area between the perpendicular walls of a step or guides, the steps or guides may interact with the polymer blocks such that, e.g., each of the alternating regions formed by the blocks is made to form a regularly spaced apart pattern with features oriented generally parallel to the walls and the horizontal surface.
Such self-assembly can be useful in forming masks for patterning features during semiconductor fabrication processes. For example, one of the alternating domains may be removed, thereby leaving the material forming the other region to function as a mask. The mask may be used to pattern features such as electrical devices in an underlying semiconductor substrate. Methods for forming a block copolymer mask are disclosed in U.S. Pat. No. 7,579,278; U.S. Pat. No. 7,723,009, and to U.S. Pat. No. 8,980,538, the entire disclosure of each of which is incorporated by reference herein.
In material processing methodologies, pattern etching can comprise the application of a thin layer of radiation-sensitive material, such as photo-resist, to an upper surface of a substrate, followed by patterning of the thin layer of material using lithographic techniques. In DSA patterning, the initial pattern is formed by the phase-separation of two or more phases present in a DSA layer, the selective removal of at least one phase using dry pattern etching, and the retention of at least one remaining phase, thereby providing a pattern for subsequent dry pattern etching. During dry pattern etching, a plasma etching process can be utilized, wherein plasma is formed from a process gas by coupling electro-magnetic (EM) energy, such as radio frequency (RF) power, to the process gas in order to heat electrons and cause subsequent ionization and dissociation of the atomic and/or molecular constituents of the process gas. Using a series of dry etching processes, the initial pattern may be formed in the DSA layer, followed by transfer of the pattern to the underlying layers within a film stack, including the one or more material layers that are desired for the end product, e.g., electronic device. To do so, the selective removal of one material relative to other material(s) is necessary. And, among other things, during the pattern transfer process, profile control for the pattern extended into underlying layers is of critical importance.
The described embodiments include performing a Capacitive Coupled Plasma (CCP)-based curing process for selective treatment, or hardening, of PS regions in PS-b-PMMA block copolymer DSA films prior to dry etch development of PMMA regions. In various embodiments, the curing chemistry can be Ar/H2, HBr, N2/H2, etc., which has the capability of generating Vacuum Ultraviolet (VUV) photon flux for polymer curing. The curing effect may enhance the etch resistance of PS regions, thereby freezing the bulk defects during plasma PMMA removal. The defects can then be measured by commonly used metrology techniques like CDSEM and quantized.
One advantage of the described methods is enhanced visibility and detection of the bulk defects, which otherwise cannot be measured. Such embodiments enable defect metrology of DSA patterning, thereby making DSA devices manufacturable, eliminating the requisite number of processing steps, and semiconductor processing, as well as reducing manufacturing time and cost. Additionally, such embodiments can be useful for quick evaluation of various BCP film materials, thereby reducing learning cycle times.
Introduction of a plasma curing step prior to removing PMMA from PS-PMMA DSA mask films may enhance etch resistance of the PS regions in the bulk of the film, thereby making bulk defects clearly visible in the form of bridging, line flops and sidewall roughness during dry plasma removal of PMMA. Without the plasma curing step prior to plasma-etch removal of PMMA from DSA films, on the other hand, the remaining PS mask margin is limited only to pattern transfer into the underlying Anti-Reflective Coating (ARC) layer. Therefore, a high selectivity process for DSA film development can be used as an alternative to a Self-Aligned Doubled Patterning (SADP) process, thereby eliminating several processing steps and making manufacturing much more cost effective for advanced technology devices. For example, such embodiments may provide additional process flexibility for patterning at sub 32 nm pitches.
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views,
Unfortunately, semiconductor devices manufactured according to DSA processes, such as those described in
One uncertainty relating to DSA processes includes defect density levels, and defect types for line/space process flows. The traditional topological defects such as dislocation and disclination defects shown in
In an embodiment, a top layer with a first material and a second material may be formed on the underlying layer(s). In the embodiment of
During the single-step etch process, without passivation, the first polymer 308, and a portion of the second polymer 310, may be removed by a sheath of etchant radicals and ions 312. In such an embodiment, portions of the neutral polymer layer 306 may be removed as well, as illustrated in
The process of
In an embodiment, the etch process includes removing the first polymer 308, and a portion of the hardened second polymer 404, but a reduced amount of the hardened second polymer 404 as compared with the amount of the hardened second polymer 310 removed in etch processes performed without the curing step. In such an embodiment, the metrology feedback may be used to control one or more integration variables in order to meet target integration objectives during one or more processes including the VUV curing process, the metrology process, and/or the etch process. In a further embodiment, the process may include at least partially transferring the pattern into the ARC layer 304.
The target integration objectives may include target LER, LWR, and Critical Dimension (CD). In some embodiments, the integration process may be used for rapid evaluation of BCP film material. Beneficially, improved integration processes may lower cost of ownership and increase substrate throughput, as compared with integration processes that do not use vacuum curing and metrology feedback. In various embodiments, operating variables of the integration process include plasma density, feed gas flow, etching time, process pressure, process temperature, and bias power. In a further embodiment, two or more of the operating variables of the film layer or region removal process may be controlled using a controller in order to meet target integration objectives. A suitable controller is described in further detail below with relation to the system of
In such an embodiment, the LER, LWR, and CD attainable allows process flexibility at sub-32 nm pitch substrates. For example, in some embodiments, the LER may be in the range of 3.00 to 3.83 nm. Similarly, the LWR may be in the range of 4.00 to 5.00 nm. In such embodiments, the CD is in the range of 13.00 to 13.80 nm. In order to achieve such results, the etch selectivity of the first polymer 308 and the hardened second polymer 404 may be in the range of 2.0 to 2.80.
As shown in the images of
On the other hand, the process with a pre-etch VUV cure step, as shown in
The cure plasma may include chemistries such as Ar/H2, HBr, N2/H2, etc., which has the capability of generating VUV photon flux for polymer curing. The curing effect may enhance the etch resistance of PS regions, thereby freezing the bulk defects during plasma PMMA removal. In such an embodiment, defect visibility with CDSEM is improved. Accordingly, the metrology process may quantify the defects made visible by the VUV curing process and generate a defect profile of the top layer. Consequently, feedback may be obtained for optimization of lithography processes, and for mitigation of further defects.
Substrate 825 can be affixed to the substrate holder 820 via a clamping system (not shown), such as a mechanical clamping system or an electrical clamping system (e.g., an electrostatic clamping system). Furthermore, substrate holder 820 can include a heating system (not shown) or a cooling system (not shown) that is configured to adjust and/or control the temperature of substrate holder 820 and substrate 825. The heating system or cooling system may comprise a re-circulating flow of heat transfer fluid that receives heat from substrate holder 820 and transfers heat to a heat exchanger system (not shown) when cooling, or transfers heat from the heat exchanger system to substrate holder 820 when heating. In other embodiments, heating/cooling elements, such as resistive heating elements, or thermo-electric heaters/coolers can be included in the substrate holder 820, as well as the chamber wall of the processing chamber 810 and any other component within the processing system 800.
Additionally, a heat transfer gas can be delivered to the backside of substrate 825 via a backside gas supply system 826 in order to improve the gas-gap thermal conductance between substrate 825 and substrate holder 820. Such a system can be utilized when temperature control of the substrate is required at elevated or reduced temperatures. For example, the backside gas supply system can comprise a two-zone gas distribution system, wherein the helium gas-gap pressure can be independently varied between the center and the edge of substrate 825.
In the embodiment shown in
In the embodiment shown in
Furthermore, the electrical bias of electrode 822 at a RF voltage may be pulsed using pulsed bias signal controller 831. The RF power output from the RF generator 830 may be pulsed between an off-state and an on-state, for example. Alternately, RF power is applied to the substrate holder electrode at multiple frequencies. Furthermore, impedance match network 832 can improve the transfer of RF power to plasma in plasma processing chamber 810 by reducing the reflected power. Match network topologies (e.g. L-type, π-type, T-type, etc.) and automatic control methods are well known to those skilled in the art.
Gas distribution system 840 may comprise a showerhead design for introducing a mixture of process gases. Alternatively, gas distribution system 840 may comprise a multi-zone showerhead design for introducing a mixture of process gases, and adjusting the distribution of the mixture of process gases above substrate 825. For example, the multi-zone showerhead design may be configured to adjust the process gas flow or composition to a substantially peripheral region above substrate 825 relative to the amount of process gas flow or composition to a substantially central region above substrate 825. In such an embodiment, gases may be dispensed in a suitable combination to form a VUV cure plasma and/or dry etch plasma within the chamber 810.
Vacuum pumping system 850 can include a turbo-molecular vacuum pump (TMP) capable of a pumping speed up to about 8000 liters per second (and greater) and a gate valve for throttling the chamber pressure. In conventional plasma processing devices utilized for dry plasma etching, an 800 to 3000 liter per second TMP can be employed. TMPs are useful for low pressure processing, typically less than about 50 mTorr. For high pressure processing (i.e., greater than about 80 mTorr), a mechanical booster pump and dry roughing pump can be used. Furthermore, a device for monitoring chamber pressure (not shown) can be coupled to the plasma processing chamber 810.
In an embodiment, the controller 855 can comprise a microprocessor, memory, and a digital I/O port capable of generating control voltages sufficient to communicate and activate inputs to processing system 800 as well as monitor outputs from plasma processing system 800. Moreover, controller 855 can be coupled to and can exchange information with RF generator 830, pulsed bias signal controller 831, impedance match network 832, the gas distribution system 840, vacuum pumping system 850, as well as the substrate heating/cooling system (not shown), the backside gas supply system 826, and/or the electrostatic clamping system 828. For example, a program stored in the memory can be utilized to activate the inputs to the aforementioned components of processing system 800 according to a process recipe in order to perform a plasma assisted process, such as a plasma etch process or a post heating treatment process, on substrate 825.
In addition, the processing system 800 can further comprise an upper electrode 870 to which RF power can be coupled from RF generator 872 through optional impedance match network 874. A frequency for the application of RF power to the upper electrode can range from about 0.1 MHz to about 200 MHz, in one embodiment. Alternatively, the present embodiments may be used in connection with Inductively Coupled Plasma (ICP) sources, Capacitive Coupled Plasma (CCP) sources, Radial Line Slot Antenna (RLSA) sources configured to operate in GHz frequency ranges, Electron Cyclotron Resonance (ECR) sources configured to operate in sub-GHz to GHz ranges, and others. Additionally, a frequency for the application of power to the lower electrode can range from about 0.1 MHz to about 80 MHz. Moreover, controller 855 is coupled to RF generator 872 and impedance match network 874 in order to control the application of RF power to upper electrode 870. The design and implementation of an upper electrode is well known to those skilled in the art. The upper electrode 870 and the gas distribution system 840 can be designed within the same chamber assembly, as shown. Alternatively, upper electrode 870 may comprise a multi-zone electrode design for adjusting the RF power distribution coupled to plasma above substrate 825. For example, the upper electrode 870 may be segmented into a center electrode and an edge electrode.
Depending on the applications, additional devices such as sensors or metrology devices can be coupled to the processing chamber 810 and to the controller 855 to collect real time data and use such real time data to concurrently control two or more selected integration operating variables in two or more steps involving deposition processes, RIE processes, pull processes, profile reformation processes, heating treatment processes and/or pattern transfer processes of the integration scheme. Furthermore, the same data can be used to ensure integration targets including completion of post heat treatment, patterning uniformity (uniformity), pulldown of structures (pulldown), slimming of structures (slimming), aspect ratio of structures (aspect ratio), line width roughness, substrate throughput, cost of ownership, and the like are achieved.
Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.
This application is related to and claims priority to U.S. Provisional Application No. 62/316,216, filed Mar. 31, 2016, the entire contents of which are herein incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5344742 | Sinta et al. | Sep 1994 | A |
| 5650261 | Winkle | Jul 1997 | A |
| 5709754 | Morinville et al. | Jan 1998 | A |
| 5830608 | Ishiwata et al. | Nov 1998 | A |
| 6303477 | Ianovitch | Oct 2001 | B1 |
| 6312971 | Amundson et al. | Nov 2001 | B1 |
| 6846748 | Chien et al. | Jan 2005 | B2 |
| 6855476 | Ferreira et al. | Feb 2005 | B2 |
| 7521094 | Cheng et al. | Apr 2009 | B1 |
| 7579278 | Sandhu | Aug 2009 | B2 |
| 7687220 | Yamato et al. | Mar 2010 | B2 |
| 7723009 | Sandhu et al. | May 2010 | B2 |
| 7754518 | Koelmel et al. | Jul 2010 | B2 |
| 7811940 | Sandhu | Oct 2010 | B2 |
| 7923373 | Sandhu | Apr 2011 | B2 |
| 8039196 | Kim et al. | Oct 2011 | B2 |
| 8083953 | Millward et al. | Dec 2011 | B2 |
| 8241822 | Yamato et al. | Aug 2012 | B2 |
| 8277564 | Le et al. | Oct 2012 | B2 |
| 8333522 | Arima et al. | Dec 2012 | B2 |
| 8420304 | Inatomi | Apr 2013 | B2 |
| 8603867 | Kim et al. | Dec 2013 | B2 |
| 8790522 | Schmid et al. | Jul 2014 | B1 |
| 8853085 | Abdallah et al. | Oct 2014 | B1 |
| 8900467 | Chapuis et al. | Dec 2014 | B1 |
| 8980538 | Somervell et al. | Mar 2015 | B2 |
| 8986554 | Kim et al. | Mar 2015 | B2 |
| 9005877 | Rathsack et al. | Apr 2015 | B2 |
| 9034197 | Lille et al. | May 2015 | B2 |
| 9190288 | Tanaka et al. | Nov 2015 | B2 |
| 9339312 | Doherty et al. | May 2016 | B2 |
| 9412611 | Somervell et al. | Aug 2016 | B2 |
| 9418860 | Somervell et al. | Aug 2016 | B2 |
| 20020192619 | Besek | Dec 2002 | A1 |
| 20020193619 | Crivello et al. | Dec 2002 | A1 |
| 20030004075 | Suto et al. | Jan 2003 | A1 |
| 20030084925 | Nakajima et al. | May 2003 | A1 |
| 20030227090 | Okabe | Dec 2003 | A1 |
| 20050056219 | Dip et al. | Mar 2005 | A1 |
| 20050215713 | Hessell et al. | Sep 2005 | A1 |
| 20050229427 | Sugimoto et al. | Oct 2005 | A1 |
| 20060123658 | Izumi | Jun 2006 | A1 |
| 20060251989 | Breyta et al. | Nov 2006 | A1 |
| 20070037412 | Dip et al. | Feb 2007 | A1 |
| 20070155132 | Ancilotti et al. | Jul 2007 | A1 |
| 20070184656 | Sherman et al. | Aug 2007 | A1 |
| 20070224823 | Sandhu | Sep 2007 | A1 |
| 20070237697 | Clark | Oct 2007 | A1 |
| 20070238028 | Inatomi | Oct 2007 | A1 |
| 20080032490 | Tuominen et al. | Feb 2008 | A1 |
| 20080193658 | Millward | Aug 2008 | A1 |
| 20080311402 | Jung et al. | Dec 2008 | A1 |
| 20080318005 | Millward | Dec 2008 | A1 |
| 20090081827 | Yang et al. | Mar 2009 | A1 |
| 20090087664 | Nealey et al. | Apr 2009 | A1 |
| 20090181171 | Cheng et al. | Jul 2009 | A1 |
| 20090200646 | Millward et al. | Aug 2009 | A1 |
| 20090215272 | Sadjadi et al. | Aug 2009 | A1 |
| 20090236309 | Millward et al. | Sep 2009 | A1 |
| 20090291398 | Horiuchi | Nov 2009 | A1 |
| 20100055621 | Hatakeyama et al. | Mar 2010 | A1 |
| 20100159214 | Hasegawa et al. | Jun 2010 | A1 |
| 20100178615 | Colburn et al. | Jul 2010 | A1 |
| 20100193898 | Hautala et al. | Aug 2010 | A1 |
| 20100200774 | Burke et al. | Aug 2010 | A1 |
| 20100227276 | Mizuno | Sep 2010 | A1 |
| 20100279062 | Millward et al. | Nov 2010 | A1 |
| 20110033786 | Sandhu | Feb 2011 | A1 |
| 20110039413 | Akinmade-Yusuff et al. | Feb 2011 | A1 |
| 20110059299 | Kim et al. | Mar 2011 | A1 |
| 20110147965 | Mistry et al. | Jun 2011 | A1 |
| 20110147984 | Cheng et al. | Jun 2011 | A1 |
| 20110147985 | Cheng et al. | Jun 2011 | A1 |
| 20110151382 | Kim et al. | Jun 2011 | A1 |
| 20110186544 | Endou et al. | Aug 2011 | A1 |
| 20110206905 | Buriak et al. | Aug 2011 | A1 |
| 20110229120 | Takaki et al. | Sep 2011 | A1 |
| 20110232677 | Liu et al. | Sep 2011 | A1 |
| 20110272381 | Millward et al. | Nov 2011 | A1 |
| 20120003587 | Kim et al. | Jan 2012 | A1 |
| 20120031892 | Shigetomi et al. | Feb 2012 | A1 |
| 20120046415 | Millward et al. | Feb 2012 | A1 |
| 20120046421 | Darling et al. | Feb 2012 | A1 |
| 20120067843 | Watanabe et al. | Mar 2012 | A1 |
| 20120077127 | Sills et al. | Mar 2012 | A1 |
| 20120088192 | Trefonas et al. | Apr 2012 | A1 |
| 20120141741 | Millward | Jun 2012 | A1 |
| 20120202017 | Nealey et al. | Aug 2012 | A1 |
| 20120207940 | Muramatsu et al. | Aug 2012 | A1 |
| 20120223053 | Millward et al. | Sep 2012 | A1 |
| 20120312501 | Koole et al. | Dec 2012 | A1 |
| 20130099362 | Kim et al. | Apr 2013 | A1 |
| 20130143406 | Hsu et al. | Jun 2013 | A1 |
| 20130183827 | Millward | Jul 2013 | A1 |
| 20130189504 | Nealey et al. | Jul 2013 | A1 |
| 20130273330 | Wang | Oct 2013 | A1 |
| 20130292805 | Cai et al. | Nov 2013 | A1 |
| 20130344249 | Minegishi et al. | Dec 2013 | A1 |
| 20140061154 | Kim et al. | Mar 2014 | A1 |
| 20140065839 | Kawanishi et al. | Mar 2014 | A1 |
| 20140099583 | Holmes et al. | Apr 2014 | A1 |
| 20140116980 | Wuister | May 2014 | A1 |
| 20140127910 | Hieno et al. | May 2014 | A1 |
| 20140154630 | Schmid et al. | Jun 2014 | A1 |
| 20140256145 | Abdallah et al. | Sep 2014 | A1 |
| 20140287083 | Gao et al. | Sep 2014 | A1 |
| 20140315390 | Abdallah et al. | Oct 2014 | A1 |
| 20150021295 | Yoshikawa et al. | Jan 2015 | A1 |
| 20150108087 | Somervell et al. | Apr 2015 | A1 |
| 20150111387 | Somervell et al. | Apr 2015 | A1 |
| 20150126034 | Latypov et al. | May 2015 | A1 |
| 20150191034 | Millward et al. | Jul 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 101578232 | Nov 2009 | CN |
| 101681812 | Mar 2010 | CN |
| 102037543 | Apr 2011 | CN |
| 103187245 | Jul 2013 | CN |
| 102012105384 | Sep 2012 | DE |
| 11030711 | Feb 1999 | JP |
| 2002163998 | Jun 2002 | JP |
| 2002265617 | Sep 2002 | JP |
| 2007100191 | Apr 2007 | JP |
| 2007279493 | Oct 2007 | JP |
| 2008036491 | Feb 2008 | JP |
| 2010085977 | Apr 2010 | JP |
| 2010527137 | Aug 2010 | JP |
| 2010531051 | Sep 2010 | JP |
| 2011018778 | Jan 2011 | JP |
| 2011515537 | May 2011 | JP |
| 2011522707 | Aug 2011 | JP |
| 2012038969 | Feb 2012 | JP |
| 2012064783 | Mar 2012 | JP |
| 2013164436 | Aug 2013 | JP |
| 200900097884 | Jan 2009 | KR |
| 20120133272 | Dec 2012 | KR |
| 9627212 | Sep 1996 | WO |
| 03016209 | Feb 2003 | WO |
| 2007127496 | Nov 2007 | WO |
| 2008097736 | Aug 2008 | WO |
| 2008150673 | Dec 2008 | WO |
| 2009100053 | Aug 2009 | WO |
| 2009117243 | Sep 2009 | WO |
| 2009142869 | Nov 2009 | WO |
| 2010042290 | Apr 2010 | WO |
| 2011036778 | Mar 2011 | WO |
| 20110140200 | Nov 2011 | WO |
| 2012071330 | May 2012 | WO |
| 2012084558 | Jun 2012 | WO |
| 2012175343 | Dec 2012 | WO |
| 20120175342 | Dec 2012 | WO |
| 2013010730 | Jan 2013 | WO |
| Entry |
|---|
| State Intellectual Property Office of People's Republic of China, English translation of Office Action issued in related CN Application No. 201380031525.5 dated Nov. 13, 2017, 12 pp. |
| Liu et al., “Integration of Block Copolymer Directed Assembly with 193 Immersion Lithography” American Vacuum Society, J. Vac. Sci. Technol. B 28(6), Nov./Dec. 2010, 5 pp. |
| Bielawski et al., “Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides,” J. Org. Chem. 73:4602-4607, 2008. |
| Cheng, et al., “EUVL Compatible, LER Solutions using Functional Block Copolymers,” Alternative Lithographic Technologies IV, Proc. of SPIE, vol. 8323, 2012, 11 pp. |
| Cupta, “Photoacid Generators for Catalytic Decomposition of Polycarbonate,” Thesis for Master of Science, Georgia Institute of Technology, 2006, 137 pp. |
| Gronheid, R.; Rincon Delgadillo, P.; Nealey, P.; Younkin, T.; Matsunaga, K.; Somervell, M. and Nafus, K. Implementations of self-assembly in a 300mm processing environment. IEEE Litho Workshop. (Jun. 25-28, 2012; Williamsburg, VA, USA). |
| Maki et al., “Photocleavable Molecule for Laser Desorption Ionization Mass Spectrometry,” J. Org. Chem. 72:6427-6433, 2007. |
| Padmanaban et al., “Application of Photodecomposable Base Concept to 193 nm Resists,” Proc. of SPIE. 3999:1136-1146, 2000. |
| Gotrik et al., “Thermosolvent Annealing of Block Copolymer Thin Films for Directed Self-Assembly Applications,” 2012 Materials Research Society (MRS) Fall Meeting & Exhibit, Symposium S: Directed Self-Assembly for Nanopatterning, Nov. 25-30, 2012, Boston, Massachussetts, 15 pp. |
| Ruebner et al., “A cyclodextrin dimer with a photocleavable linker as a possible carrier for the photosensitizer in photodynamic tumor therapy,” PNAS. 96(26):14692-14693, 1999. |
| Skulski, “Organic Iodine(I, III, and V) Chemistry: 10 Years of Development at the Medical University of Warsaw, Poland,” Molecules. 5:1331-1371, 2000. |
| Weissman et al., “Recent advances in ether dealkylation,” Tetrahedron. 61:7833-7863, 2005. |
| Hammersky et al., “Self-Diffusion of a Polystyrene-Polyisoprene Block Copolymer,” Journal of Polymer Science: Part B: Polymer Physics. 34:2899-2909, 1996. |
| Jung et al., “A Path to Ultranarrow Patterns Using Self-Assembled Lithography,” Nano Lett. 10:1000-1005, 2010. |
| Tavakkoli K.G. et al., “Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films,” Science, 336:1294-1298, 2012. |
| Cushen et al., “Oligosaccharide/Silicon-Containing Block Copolymers with 5 nm Features for Lithographic Applications” ACS Nano, vol. 6, No. 4, 2012, pp. 3424-3433. |
| Dean, et al., “Orientation Control of Silicon-containing Block Copolymer Films,” Dept. of Chemical Engineering, The University of Texas at Austin, 1 p. |
| Jarnagin, et al., “Investigation of High c Block Copolymers for Directed Self-Assembly: Synthesis and Characterization of PS-b-PHOST,” Alternative Lithographic Technologies IV, Proc. of SPIE, vol. 8323, 2012, 9 pp. |
| Steven J. Lickteig et al., Optimization of an Integrated and Automated Macro Inspection System for the Utilization of Wafer Color Variation Detection in a Photolithography Cluster, Metrology, Inspection, and Process Control for Microlithography, Proc. of SPIE vol. 6152, 9 pages. |
| Peng et al., “Development of Nanodomain and Fractal Morphologies in Solvent Annealed Block Copolymer Thin Films”, Macromolecular Rapid Communications 2007, 28, 1422-1428. |
| Korean Intellectual Property Office, English translation of Office Action issued in related KR Application No. 10-2016-7013298 dated Sep. 14, 2017, 11 pp. |
| Korean Intellectual Property Office, Office Action issued in related Korean Patent Application No. 10-2016-7013228 dated Jan. 24, 2018, 6 pp. including English translation. |
| Number | Date | Country | |
|---|---|---|---|
| 20170287790 A1 | Oct 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62316216 | Mar 2016 | US |