Douglas Mckenzie

New spin-on metal hardmask materials for lithography processes

Since the critical dimensions in integrated circuit (IC) device fabrication continue to shrink below 32 nm, multilayer stacks with alternating etch selectivities are required for successful pattern transfer from the exposed photoresist to the substrate. Inorganic resist underlayer materials are used as hard masks in reactive ion etching (RIE) with oxidative gases. The conventional silicon hardmask has demonstrated good reflectivity control and reasonable etch selectivity. However, some issues such as the rework of trilayer stacks and cleaning of oxide residue by wet chemistry are challenging problems for manufacturability. The present work reveals novel spin-on underlayer materials containing significant amounts of metal oxides in the film after baking at normal processing conditions. Such an inorganic metal hardmask (MHM) has excellent etch selectivity in plasma etch processes of the trilayer stack. The composition has good long term shelf life and pot life stability based on solution LPC analysis and wafer defect studies, respectively. The material absorbs DUV wavelengths and can be used as a spin-on inorganic or hybrid antireflective coating to control substrate reflectivity under DUV exposure of photoresist. Some of these metal-containing materials can be used as an underlayer in EUV lithography to significantly enhance photospeed. Specific metal hard masks are also developed for via or trench filling applications in IRT processes. The materials have shown good coating and lithography performance with a film thicknesses as low as 10 nm under ArF dry or immersion conditions. In addition, the metal oxide films or residues can be partially or completely removed by using various wet-etching solutions at ambient temperature.

Etching spin-on trilayer masks

Spin-on trilayer materials are increasingly being integrated in high density microfabrication that use high NA ArF lithography due to dwindling photoresist film thicknesses, lower integration cost and reduced complexity compared to analogous CVD stacks. To guide our development in spin-on trilayer materials we have established etch conditions on an ISM etcher for pattern transfer through trilayer hard masks. We report here a range of etch process variables and their impact on after-etch profiles and etch selectivity with AZ trilayer hard mask materials. Trilayer pattern transfer is demonstrated using 1st and 2nd minimum stacks with various pattern types. Etch recipes are then applied to blanket coated wafers to make comparisons between etch selectivities derived from patterned and blanket coated wafers.

Progress in spin-on metal oxide hardmask materials for filling applications

It is well known that metal oxide films are useful as hard mask material in semiconductor industry for their excellent etch resistance against plasma etches. In the advanced lithography processes, in addition to good etch resistance, they also need to possess good wet removability, fill capability, in high aspect ratio contacts or trenches. Conventional metal containing materials can be applied by chemical vapor deposition (CVD) or atomic layer deposition (ALD). Films derived from these techniques have difficulty in controlling wet etch, have low throughput and need special equipment. This leads to high costs. Therefore it is desirable to develop simple spin-on coating materials to generate metal oxide hard masks that have good trench or via filling performances using spin track friendly processing conditions. In this report, novel spin-on type inorganic formulations providing Ti, W, Hf and Zr oxide hard masks will be described. The new materials have demonstrated high etch selectivity, good filling performances, wet removal capability, low trace metals and good shelf-life stability. These novel AZ® Spin-on metal hard mask formulations can be used in several new applications and can potentially replace any metal, metal oxide, metal nitride or silicon-containing hard mask films currently deposited using CVD process in the semiconductor manufacturing process.

Reworkable Spin-on Trilayer Materials: Optimization of Rework Process and Solutions for Manufacturability

Trilayer stacks with alternating etch selectivity were developed and extensively investigated for high NA immersion lithography at 32nm node and beyond. The conveyance of pattern transfer function from photoresist to Si-containing bottom anti-reflective coating (Si-BARC) and carbonrich underlayer hard-mask (UL) elegantly solved the small etch budget issue for ultra-thin photoresists in immersion lithography. However, due to the hybrid nature of Si-BARC, many different behaviors were observed in comparison to conventional BARC. Lithographic performance, stability, and reworkability were among the most challenging issues for trilayer scheme. Despite of the rapid improvement in lithographic performance and stability of trilayer materials reported by several papers, the rework and cleaning of trilayer materials by wet chemistry remained a challenging problem for manufacturability. The dual function requirement of reflection control and pattern transfer (i.e. hard-masking) for spin-on Si-BARC mandates hybrid materials. Si-BARC containing both organic moiety and inorganic backbone were extensively studied and demonstrated excellent performance. However, the hybrid nature of Si-BARC necessitates the revisit of different wet chemistries and process adjustment is essential to achieve desirable results. In addition, the similarity in chemical structures between Si-BARC and low-κ dielectrics demands subtle rework differentiation by wet chemistry from a chemistry point of view. In our development, we strived to identify rework solutions for trilayer materials in both front-end-of-line (FEOL) and back-end-of-line (BEOL) applications. Rework solutions including diluted HF, Piranha, and low-κ compatible strippers were extensively investigated. The optimization of solution mixture ratios and processing conditions was systematically studied. Thorough defect inspection after rework was performed to ensure the readiness for manufacturability. Extensive Piranha rework study on stack wafers and monitor wafers were carried out and excellent results are reported.

Spin-on trilayer approaches to high NA 193nm lithography

New challenges face ArF bottom antireflection coatings (BARCs) with the implementation of high NA lithography and the concurrent increase use of spin-on hard masks. To achieve superior reflectivity control with high NA at least two semi-transparent ARC layers, with distinct optical indices, are necessary to effectively lower substrate reflectivity through a full range of incident angles. To achieve successful pattern transfer, these layers in conjunction with the organic resist, should be stacked with an alternating elemental composition to amplify vertical resolution during etch. This will circumvent the inherent low etch resistance of ArF resist and the decreasing film thicknesses that accompanies increasing NA. Thus, incorporating hard mask properties and antireflection properties in the same two layer system facilitates pattern transfer as a whole rather than just enhancing lithography. As with any material expected to exhibit multiple roles there is a delicate balance between optimizing materials with respect to one of its roles while not impairing its other roles. We will discuss some of these conflicts and present Si-BARCs and carbon rich underlayers which aim to balance these conflicts. In this paper we will explore simulations aimed at finding the best film thicknesses and optical indices, etch rate selectivity, and lithographic performance of high silicon content and high carbon content BARC materials designed to meet the demands of both high NA lithography and trilayer processing.

Development of spin-on-carbon hard mask for advanced node

Spin-on-carbon (SOC) hard mask is useful for multilayer lithography process because of its high etch resistance, low cost of ownership, low defectivity, high alignment accuracy, good gap filling and planarization for topography. SOC is a high carbon containing polymer solution and as a coating material, the polymers need to be soluble in organic solvent and insoluble after curing for coating upper layer materials. High carbon content (>80%) of SOC is very important for good etch resistance. As the semiconductor industry is moving to 2X nm node and beyond, further improvement of SOC properties mentioned above is required to achieve higher resolution. We synthesized a series of novel monomers and high carbon polymers applicable for SOC applications of advanced nodes. The optimized SOC was a PGMEA based formulation, had high carbon content 90%, excellent filling/leveling properties, and adequate etching properties applicable to trilayer process. The SOC successfully transferred patterns from resist into substrate and the SOC patterns did not show deformation or wiggling down to CD 40nm. This paper describes some of the SOC polymer chemistry and the performance of an optimized SOC formulation.

Spin-on metal oxide materials for N7 and beyond patterning applications

There is a growing interest in new spin on metal oxide hard mask materials for advanced patterning solutions both in BEOL and FEOL processing. Understanding how these materials respond to plasma conditions may create a competitive advantage. In this study patterning development was done for two challenging FEOL applications where the traditional Si based films were replaced by EMD spin on metal oxides, which acted as highly selective hard masks. The biggest advantage of metal oxide hard masks for advanced patterning lays in the process window improvement at lower or similar cost compared to other existing solutions.

Spin-on metal oxide materials with high etch selectivity and wet strippability

Metal oxide or metal nitride films are used as hard mask materials in semiconductor industry for patterning purposes due to their excellent etch resistances against the plasma etches. Chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques are usually used to deposit the metal containing materials on substrates or underlying films, which uses specialized equipment and can lead to high cost-of-ownership and low throughput. We have reported novel spin-on coatings that provide simple and cost effective method to generate metal oxide films possessing good etch selectivity and can be removed by chemical agents. In this paper, new spin-on Al oxide and Zr oxide hard mask formulations are reported. The new metal oxide formulations provide higher metal content compared to previously reported material of specific metal oxides under similar processing conditions. These metal oxide films demonstrate ultra-high etch selectivity and good pattern transfer capability. The cured films can be removed by various chemical agents such as developer, solvents or wet etchants/strippers commonly used in the fab environment. With high metal MHM material as an underlayer, the pattern transfer process is simplified by reducing the number of layers in the stack and the size of the nano structure is minimized by replacement of a thicker film ACL. Therefore, these novel AZ® spinon metal oxide hard mask materials can potentially be used to replace any CVD or ALD metal, metal oxide, metal nitride or spin-on silicon-containing hard mask films in 193 nm or EUV process.

Spin-on trilayer scheme: enabling materials for extension of ArF immersion lithography to 32nm node and beyond

Trilayer stacks with alternating etch selectivity were developed and extensively investigated for high NA immersion lithography at 32nm node and beyond. This paper discusses the fundamental aspects of the Si-containing BARC (Si-BARC) materials with ultra-high silicon content and carbon-rich underlayers that we developed. Designing of materials at a molecular level is presented. It was demonstrated that this fundamental understanding assisted in achieving satisfactory shelf life and excellent coating defect results. Prolith® simulations using trilayer stacks showed superior reflectivity control for hyper-NA immersion lithography. The impact of high incident angles on substrate reflectivity was analyzed and this paper demonstrated that trilayer scheme provides wider process windows and is more tolerant to topography than conventional single layer BARC. Extensive resist compatibility investigation was conducted and the root causes for poor lithography results were investigated. Excellent 45nm dense lines performance employing the spin-on trilayer stack on a 1.2 NA immersion scanner is reported. In addition, pattern transfers were successfully carried out and the Si-BARC with high silicon content demonstrated outstanding masking property. In comparison to the theoretical %Si values, better correlation with etch selectivity was observed with experimental %Si. Furthermore, this paper addresses the wet rework of trilayer materials and results using Piranha rework are presented. Clean 12in wafers were obtained after reworking trilayer stacks, as evidenced by defect analysis.

Versatility in lithographic performance of advanced 193 nm contact hole resist

This paper introduces high performing contact hole resist targeting 65 nm node and below IC applications. Both 80 nm and 100 nm contact hole performance are evaluated under optimized condition by ProlithTM simulations and the advantage of the shrinking technique (RELACSTM) is discussed for 65 nm node. The functionality of 193 nm polymers and the influence of resist components on lithographic performance are described with experimental design. The optimized resist, AZ® AX2050P is versatile in lithographic performance with large process window, excellent resist profile, good contact circularity and sidewall roughness. Its unusual PEB sensitivity property, resist pattern thermal flow behavior and performance with RELACSTM material are also reported. AZ® AXTM2050P has a high resolution combined with a large depth of focus and an iso-dense overlap window with RELACSTM R602 [85 nm CD (NA 0.85) DOF 0.30 μm @ Exposure latitude 8%].