Latest developments in EUV photoresist evaluation capability at Shanghai Synchrotron Radiation Facility

Evaluating the comprehensive characteristics of extreme ultraviolet(EUV)photoresists is crucial for their application in EUV lithography,a key process in modern technology.This paper highlights the capabilities of the Shanghai Synchrotron Radiation Facility(SSRF)08U1B beamline in advancing this field.Specifically,it demonstrates how this beamline can create fringe patterns with a 15-nm half-pitch on a resist using synchrotron-based EUV lithography.This achievement is vital for evaluating EUV photoresists at the advanced 5-nm node.We provide a detailed introduction to the methods and experimental setup used at the SSRF 08U1B beamline to assess an EUV photoresist.A significant part of this research involved the fabrication of high-resolution hydrogen silsesquioxane mask gratings.These gratings,with an aspect ratio of approximately 3,were created using electron beam lithography on an innovative mask framework.This framework was crucial in eliminating the impact of zeroth-order light on interference patterns.The proposed framework propose offers a new approach to mask fabrication,particularly beneficial for achromatic Talbot lithography and multicoherent-beam interference applications.

Use of Cucurbita pepo Oil to Fight against the UV Action on the Skin

Skin aging is a process most often attributed to UV [1] and also to the use of creams and other cosmetic products low in antioxidant compounds [2]. Photochemically stable pepo Cucurbita oil can be used as an exogenous cosmetic supplement due to its high antioxidant content. Incorporated in an agar, media containing a synthetic melanin solution with added pumpkin oil are subjected to UV light, the aging thus modeled is followed by the measurement of photoresistance values correlated with chemical and spectrophotometric analyses. This study confirms that pumpkin oil is highly effective in protecting the skin, especially the most sensitive skins such as babies’ skin [3] by reinforcing the action of melanin and also that of albinos without melanin. Indeed its SPF (Significant Sun Protection Factor) index estimated during this work is very consistent, i.e. more than 22% of UVB (280 - 315 nm) radiations are suppressed.

HYPERBRANCHED CONJUGATIVE MACROMOLECULES CONSTRUCTED FROM TRIPLE-BOND BUILDING BLOCKS

Polycyclotrimerization and polycoupling of acetylenic monomers respectively furnish hyperbranched polyarylenes and polyynes with high molecular weights （up to 1 × 10^6） in high yields （up to 99.9%）. The polymers possess low intrinsic viscosities and high thermal stabilities, losing little of their weights when heated to 〉 400℃. Upon pyrolysis at 〉 800℃, the polymers graphitize with high char yields （up to 86%）. Hyperbranched polyarylenes efficiently emit deep-blue to blue-green lights with fluorescence quantum yields up to 98% and strongly attenuate intense laser pulses with optical power-limiting performances superior to that of C60, a well-known optical limiter. Poly（alkenephenylenes）, poly（aroylarylenes） and polyynes are readily cross-linkable by UV irradiation, serving as excellent photoresist materials for the generation of patterns with nanometer resolution. Thin films of hyperbranched polyynes exhibit very high refractive indexes （n up to 1.86）. The internal and terminal acetylene moieties of the polyynes readily form complexes with cobalt carbonyls, which can be transformed into soft ferromagnetic ceramics with high magnetic susceptibilities （Ms up to ca. 118 emu/g） and near-zero magnetic losses.

Synthesis and Properties of UV-curable Hyperbranched Polyurethane and Its Application in the Negative-type Photoresist

UV-curable hyperbranched polyurethane （UV-HBPU） containing carboxyl groups was synthesized from isophorone diisocyanate （IPDI）, diethanolamine （DEOA）, polyethylene glycol （PEG-400）, hydroxyethyl acrylate （HEA）, and 2,2-his （hydroxymethyl） propionic acid （DMPA）. The UV-HBPU was used as a negative-type photoresist for a printed circuit board （PCB）. Fourier-transform infrared spectroscopy （FTIR） and proton nuclear magnetic resonance （1HNMR） spectroscopy of UV-HBPUs indicated that the synthesis was successful. Differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA） showed that the thermal stability of the UV-HBPUs decreased as the HEA content increased. The polymer exhibited excellent photoresist properties, and the resolution of circuits based on this negative-type photoresist reached 10 μm.

Research on the process of fabricating a multi-layer metal micro-structure based on UV-LIGA overlay technology

In this paper,we report the study of the process of fabricating a multi-layermetal micro-structure using UV-LIGA overlay technology,includingmask fabrication,substrate treatment,and UV-LIGA overlay processes.To solve the process problems in the masking procedure,the swelling problemof the first layer of SU-8 thick photoresist was studied experimentally.The 5μmline-width compensation and closed 20μmand 30μmisolation strips were designed and fabricated around the micro-structure pattern.The pore problemin the Ni micro-electroforming layer was analyzed and the electroforming parameters were improved.The pH value of the electroforming solution should be controlled between 3.8 and 4.4 and the current density should be below 3 A/dm^2.To solve the problems of high inner stress and incomplete development of the micro-cylinder hole array with a diameter of 30μm,the lithography process was optimized.The pre-baking temperature was increased via gradient heating and rose every 5℃ from 65℃ to 85℃ and then remained at 85℃ for 50 min–1 h.In addition,the full contact exposure was used.Finally,a multi-layer metal micro-structure with high precision and good quality of microelectroforming layer was fabricated using UV-LIGA overlay technology.

Simulations of Ion Behaviors in a Photoresist Trench During Plasma Etching Driven by a Radio-Frequency Source

Ion＇s behavior plays an important role in plasma etching processes and is determined by the local electric potential in the etched trenches. In this study, with the trench powered by a radio frequency （rf） source, the Laplace equation is solved to obtain the electric potential. The ion trajectories and the ion energy distribution （IED） at the bottom of the trench are obtained self-consistently by tracking the ions in the trench. The results show that the aspect ratio of depth- to-width of the photoresist trench and the voltage amplitude of the rf source applied to the electrode are important parameters. The larger the aspect ratio and the smaller the amplitude are, the more ions hit the sidewalls, which results in a notching phenomenon. Meanwhile, there are a higher high-energy peak and a lower low-energy peak in the IED with the increase in aspect ratio.

The Variables and Invariants in the Evolution of Logic Optical Lithography Process

Photolithography has been a major enabler for the continuous shrink of the semiconductor manufacturing design rules.Throughout the years of the development of the photolithography,many new technologies have been invented and successfully implemented,such as image projection lithography,chemically amplified photoresist,phase shifting mask,optical proximity modeling and correction,etc.From 0.25μm technology to the current 7 nm technology,the linewidth has been shrunk from 250 nm to about 20 nm,or 12.5 times.Although imaging resolution is proportional to the illumination wavelength,with the new technologies,the wavelength has only been shrunk from 248 nm to 134.7 nm(193 nm immersion in water),less than 2 times.Would it mean that the imaging performance has been continuously declining?Or we have yet fully utilized the potential of the photolithography technology?In this paper,we will present a study on the key parameters and process window performance of the image projection photolithography from 0.25μm node to the current 7 nm node.

Acidic Polyester Imides as Thermally Stable Binder Polymers for Negative-Tone Black Photoresist

Polyimides are well-known for their high chemical inertness and thermal stability. However, it is usually challenging to synthesize UV-curable polyimides since the imidization reaction requires such harsh conditions that acrylate type double bonds cannot withstand. In this work, synthetic methods are developed to obtain polyester-imide type binder polymers with high thermal stability, high compatibility with the other components of the black photoresist, and fine photolithographic patterning property for the negative-tone black photoresist. The syntheses of diimide-diacid or diimide-diol intermediates for the polyesterification with dianhydride gave polyester imides which meets this requirement. The photolithographic tests have shown that the patterning of the micron-sized PDL of the organic light emitting diode (OLED) panel could be obtained. This work will interest the researchers working on the design and optimization of thermally stable binder polymers.

Recent Advances in Organic-inorganic Hybrid Photoresists

Photoresists are radiation-sensitive materials used for forming patterns to build up IC devices.To date,most photoresists have been based on organic polymers,which have been dominating the semiconductor industries over the past few decades.It is obvious that extreme ultraviolet(EUV)lithography has become the next-generation lithography technology.The development of comprehensive performance EUV resist is one of the most critical issues.However,organic polymeric photoresists are difficult to meet the harsh requirements of EUV lithography.Pure inorganic photoresists such as metal salts,hydrogen silsesquioxane(HSQ)are expected for EUV lithography due to their high resistance and high resolution.But the low sensitivity makes them not suitable for high volume manufacturing(HVM).Organic-inorganic hybrid photoresists,containing both organic and inorganic components,are regarded as one of the most promising EUV resists.They combine both merits of organic and inorganic materials and have significant advantages in machinability,etching resistance,EUV absorption,and chemical/thermal stability.Organic-inorganic hybrid photoresists are considered as ideal materials for realizing industrialgrade patterns below 10 nm.This review mainly focuses on the development of organic-inorganic hybrid photoresists over the past decade.

COPOLYMERS OF CHLOROETHYL METHACRYLATE, GLYCIDYL METHACRYLATE, AND METHYL METHACRYLATE AS SYNCHROTRON RADIATION x-RAY PHOTORESISTS

The copolymers of chloroethyl methacrylate (CMA), glycidyl methacrylate (GMA), and methyl methacrylate (MMA) were synthesized in benzene solution. Their breadths of the molecular weight distributions are 2.1 and 2.3, respectively. The thermal stability of P(GMA-CMA) is superior to that of P(CMA-MMA). The resolutions of P(CMA-MMA) and P(GMA-CMA) photoresists were found to be 0.1-0.16 mu m and 0.17-0.2 mu m, respectively. (Author abstract) 9 Refs.

SYNTHESIS AND THERMAL PROPERTIES OF A NEW CHOLIC ACIDCONTAINING COPOLYMER

A new copolymer was synthesized by free radical polymerization in solution from methyl 3α-methylacryloyl-7α, 12α-dihydroxy-5β-cholan-24-oate (MACAME) and maleic anhydride (MAN). The copolymer was characterized by FT-IR and functional group analysis. The reactivity ratios of the two monomers were estimated [r_1 = 11.6 (MACAME), r_2 = 0.01(MAN)] by conducting a series of copolymerizations with a variety of monomer feed compositions and analyzing thecopolymer composition. Thermogravimetric and differential scanning calorimetric analyses of the samples indicate that thecopolymer possesses good thermal stability. The temperature at which the copolymer samples experienced a 10% weight loss(T_(WL)) is over 287℃, and the T_g ranged from 174 to 185℃ for the copolymers.

Research on the Mechanism of Multilayer Reactive Ion Etching

Dry etching has now become one of the key processes of high ratio of depth to width microstructure and fine patterning. This paper presents a new dry etching technology - multilayer reactive ion etching technology （MRIE）. By taking full advantage of the spatial layout of the chamber, arranging multi-layer electrodes and transporting the discharged gas by a layered air supply device, the function of simultaneous etching in every reaction chamber （layer） is realized. This method can significantly enhance the productivity. Taking the photoresist etching by MRIE as an example, the law and mechanism influencing the etching rate and uniformity were analyzed for different conditions. The result shows that when plate distance is 50/55/60 mm （from bottom to top）, and vacuum degree, ratio of O2 to Ar, RF source power, and continuous etching time are respectively 40 Pa, 1/2, 600 W, and 20 min, the optimal process is achieved. The average etching rate and uniformity are 143.93 A/min and 9.8%, respectively.

Optimum design of photoresist thickness for 90-nm critical dimension based on ArF laser lithography

In this work, a 90-nm critical dimension （CD） technological process in an ArF laser lithography system is simulated, and the swing curves of the CD linewidth changing with photoresist thickness are obtained in the absence and presence of bottom antireflection coating （BARC）. By analysing the simulation result, it can be found that in the absence of BARC the CD swing curve effect is much bigger than that in the presence of BARC. So, the BARC should be needed for the 90-nm CD manufacture. The optimum resist thickness for 90-nm CD in the presence of BARC is obtained, and the optimizing process in this work can be used for reference in practice.

Fabrication of Diffraction-limited Full Aperture Microlens Array by Melting Photoresist

A further study on the fabrication of diffraction--limited full aperture microlens array by melting photoresist is described. The formation of aspherical surface is considered. The parameters for controlling the process of lens production, the height of original photoresist cylinders and the angle of contact between the melted photoresist and the substrate, are discussed in detail. The diffraction limited full--aperture microlens arrays have been obtained,and some measurement results are shown in the paper. A method of controlling the formation of quality microlens array in real time is suggested.

Laser Produced Plasma X-Ray Sources for Nanoscale Resolution Contact Microscopy: A Candidate in Cancerous Stem Cells Imaging

Plasma X-ray sources for biological microscopy have been produced by focusing single shots from Nd:glass laser onto carbon rod targets at irradiances between 1 × 1013 W⋅cm−2 and 3 × 1013 W⋅cm−2 to expose test objects. The optimum parameters needed for obtaining high accurate information on the samples under test namely: the minimum energies and irradiances at a range of angles between the incoming laser beam and the normal to the resist, the depth of exposure of the photoresist as a function of incident laser energy (and irradiance) were concluded in this work.

Epoxy Methacrylate Resin as Binder Polymer for Black Negative-Tone Photoresists

Epoxy acrylate (EA) resin, which originates from epoxides, has long been served as a photocurable coating and adhesive material owing to its double bonds. Specifically, alkaline-developable EA resins can be used as a binder polymer in negative-tone photoresists. In this work, we synthesized a series of acidic polyester-type epoxy methacrylate resins, characterized the intermediates and products, and tested their performance as a binder polymer for the photolithographic micro-patterning of the pixel-defining layer on organic light-emitting diodes in comparison to a widely used commercial binder polymer. Copolymer-type binder polymer BP-2-2 was produced excellent patterning with no residue due to its high compatibility with the black mill base.

Alkenyl-type ligands functionalized tin-lanthanide oxo nanoclusters as molecular lithography resists

Both the cluster chemistry of tin and lanthanides have attracted extensive research interest,showing wide applications in catalysis,magnetism,luminescence,and lithography.However,their fusion into heterometallic Sn-Ln oxo clusters is still to be explored.In this study,through the stabilization of alkenyl-type cis-5-norbornene-endo-2,3-dicarboxylic acid(H_(2)NE)ligands,a series of atomically precise Sn-Ln oxo nanoclusters have been successfully constructed from the assembly of heterometallic tetranuclear Sn_(x)Ln((4-x))building blocks.Thereinto,Sn_(12)Eu_(8) and Sn_(13)Er_(6) with the highest nuclearities are built from multiple assembly of 8{Sn_(2)Eu_(2)}units and 6{Sn_(3)Er}and{Sn_(2)Er_(2)}units,respectively.ESI-MS analysis indicates that Sn_(13)Er_(6) has high solution stability,allowing their packing into thin films for lithography applications.As a result of electron beam lithography(EBL)studies,the condensation of Sn_(13)Er_(6) can be triggered by low energy radiation of 10μC/cm^(2),and 50 nm lines have been fabricated at expose energy of 50μC/cm^(2),confirming the satisfying sensitivity and resolution of Sn_(13)Er_(6).Hence,the success of this study develops the chemistry of heterometallic tin-lanthanide clusters that can be applied as novel negative photoresist materials.

Generating Microstructures with Highly Variable Mechanical Performance using Two-Photon Lithography and Thiol-ene Photopolymerization

In this study,we investigate the effect of the exposure dose on the mechanical property of the photoresins generated with acrylate self-polymerization and thiol-ene polymerization.The results indicate that the mechanical performance of the thiol-ene photoresin is highly depended on the exposure dose during the solidification process.With 350-fold exposure dose change,the stiffness of the thiol-ene photoresin reached more that 700-fold change compare to 14-fold of the acrylate photoresin.We developed a TPL photoresist based on our results and show the capability to fabricate microstrucutres with high resolution and variable mechanical performances using this method.

CIGS异质结中的侧向双极性光电阻效应及其在光位敏探测器和存储器中的应用

CIGS异质结中存在侧向光伏效应,并且由于光照区域和非光照区域间载流子浓度的不同,会产生扩散运动及扩散流.利用该扩散载流子对外加偏压下漂移载流子的散射作用,成功实现了侧向光电阻效应,该效应可用于开发基于光电阻调控的新型光位敏探测器.该结构侧向光电阻响应光谱范围为330~1150 nm,位置灵敏度达63.26Ωmm-1,非线性度<4.5%,响应速度为14.46 ms(上升)和14.52 ms(下降).另外,考虑到不同光照位置处电阻的差异,该效应还可用于开发平面高密度光控的电阻存储器件.不同位置处电阻大小可通过外加偏压、光功率密度和光波长等条件进行有效调控,且均表现出很好的稳定性,存储密度可达1μm.最后,通过载流子扩散和漂移作用模型,对上述现象的产生和调控机理进行了解释.该研究提出了基于侧向光电阻调控的光位敏探测器和存储器的新方法,揭示了CIGS异质结的一种新应用;同时为其他材料或结构在开发光电阻为基础的探测和存储器件方面提供了新思路.

Electrochemical micromachining of micro-dimple arrays on cylindrical inner surfaces using a dry-film photoresist

The application of surface textures has been employed to improve the tribological performance of various mechanical components. Various techniques have been used for the application of surface textures such as micro-dimple arrays, but the fabrication of such arrays on cylindrical inner surfaces remains a challenge. In this study, a dry-film photoresist is used as a mask during through-mask electrochemical micromachining to successfully prepare micro-dimple arrays with dimples 94 lm in diameter and 22.7 lm deep on cylindrical inner surfaces, with a machining time of 9 s and an applied voltage of 8 V. The versatility of this method is demonstrated, as are its potential low cost and high efficiency. It is also shown that for a fixed dimple depth, a smaller dimple diameter can be obtained using a combination of lower current density and longer machining time in a passivating sodium nitrate electrolyte.