Salem K. Mullen

EUV underlayer materials for 22nm HP and beyond

EUV lithography is expected to be an important technology for manufacturing 22 nm node and beyond in the semiconductor industry. To achieve the desired resist RLS performance for such fine feature patterns, multilayer materials are almost certainly needed to define the overall lithography process. The resist modeling and experiment studies suggest high EUV absorbance of the film improves resolution, line width roughness and sensitivity. In this paper, we report the studies of new EUV underlayers (EBL) based on crosslinkable organic underlayer materials with high EUV photon absorption (EPA) unit. The lithography results for the new EUV underlayer materials have demonstrated advantages over conventional organic underlayer in terms of resist sensitivity, resolution, process window, pattern profile, collapse margin, and possibly line width roughness.

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.

Second-generation radiation sensitive developable bottom anti-reflective coatings (DBARC) and implant resists approaches for 193-nm lithography

We will discuss our approach towards a second generation radiation sensitive developable bottom antireflective coating (DBARCs) for 193 nm. We will show imaging results (1:1 L/S features down to 140 nm) for some first generation implant resist material based upon a fluorinated resins and also show relative implant resistance of these first generation fluorinated resists towards As implantation (15 KeV at 5x1015 dose with 20 x 10-4 amp). Also, discussed will be a second generation of implant resists based on a non-fluorinated resins. Surprisingly, we found that the nonfluorinated materials gave better implant resistance (~2-3 X1011 atoms/cm2) despite the higher atomic number of fluorine compared to hydrogen in the fluorinated implant materials (~2-5X1012 atoms/cm2). Finally, we will give an update on the lithographic performance of this second generation of implant resists.

Organic ArF bottom anti-reflective coatings for immersion lithography

Substrate reflectivity control plays an important role in immersion lithography. Multilayer bottom anti-reflective coatings (B.A.R.C.s) become necessary. This paper will focus on the recent development in organic ArF B.A.R.C. for immersion lithography. Single layer low k ArF B.A.R.C.s in conjunction with multilayer CVD hard mask and dual layer organic ArF B.A.R.C. application will be discussed. High NA dry and wet lithography data will be presented. We will also present the etch rate data, defect data and out-gassing property of these new B.A.R.C. materials.

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.

Novel spin-on metal hardmask materials for filling applications

Hardmasks are indispensable materials during pattern transfer to the desired substrates in the semiconductor manufacturing process. Primarily there are two types of hardmask materials - organic and inorganic - and they can be coated onto substrates or underlying materials either by a simple spin-on process or by more expensive methods such as chemical vapor deposition (CVD), atomic layer deposition (ALD) and sputtering process. Most inorganic hardmasks such as SiO2, SiON, SiN and TiN are deposited using the CVD process. Future nodes require hardmasks with high etch resistance as the designs move from horizontal to vertical (3D). We have reported novel spin-on metallic hardmasks (MHM) with comparable or higher etch resistance than SiO2.1-2 In addition to high etch resistance, they are easy to remove using wet etch chemicals. The spin-on process offers high throughput and commonly used spin tracks can be utilized; thereby reducing overall process costs when compared with CVD. Via-fill performance is also an important attribute of hardmask materials for these future nodes. Organic spin-on materials, both siloxane- and carbon-based, are used in filling applications of deep via or deep trench fill, such as those found in LELE double-patterning schemes. Inorganic materials deposited by either chemical vapor deposition (CVD) or atomic layer deposition (ALD) have higher resistance to oxygenated plasma than organic materials, but are hindered by their poor filling performance. Therefore, novel tungsten (W) containing MHM materials having both good filling performance and higher resistance to oxygenated plasma than organic materials would be of value in some filling applications. The present paper describes specific metal oxides useful for filling applications. In addition to basic filling performance and etch resistance, other properties such as optical properties, outgas and shelf life via forced aging etc. will be discussed.

All i-line lift-off T-gate process and materials

An all i-line 0.22 um T-gate process is demonstrated. A resist structure suitable for metal deposition and lift-off is constructed sequentially with two different resist materials. The lithographic process is described in details in this paper.

Underlayer and rinse materials for improving EUV resist performance

Photoresists play a key role in enabling the patterning process, and the development of their chemistry has contributed significantly to the industry’s ability to continue shrinking device dimensions. However, with the increasing complexity of patterning ever smaller features, photoresist performance needs to be supported by a large number of materials, such as antireflective coatings and anti-collapse rinses. Bottom anti-reflective coatings are widely used to control reflectivity-driven pattern fidelity in i-line and DUV exposures. While no such reflectivity control is required at EUV wavelengths, it has been demonstrated that use of an EUV underlayer (EBL) coating with high EUV photon absorption (EPA) unit can improve resist performance such as sensitivity and resist-substrate poisoning, thereby improving resolution and process window. EBL can also help to reduce the effect of out-of-band (OoB) irradiation. Traditionally, final photoresist image cleaning after the develop step has been performed using de-ionized water, generally known as a “rinse step”. More recently pattern collapse has developed to a major failure mode in high resolution lithography attributed to strong capillary forces induced by water resulting in pattern bending (‘pattern sticking’) or adhesion failure. With decreasing feature geometries (DPT immersion lithography, EUV) the benefit of rinse solutions to prevent pattern collapse has increased. In addition such rinse solutions can in some cases improve defects and LWR. In this paper we describe the advantages of AZ® EBL series of EUV underlayer materials and EUV FIRM® EXTREME™ rinse solutions when applied individually and in combinations. It is demonstrated that the use of underlayer materials can help improve LWR through improvement of resist profiles. Use of FIRM® EXTREME™ rinse is shown to provide significant improvement in collapse margin and total defect counts.

High-etch-rate low-bias bow outgassing BARC via-filling materials for 193-nm ArF lithographic process

As critical dimensions in integrated circuit (IC) device fabrication continue to shrink to less than 90 nm, designing multi-functional organic bottom anti-reflective coating (BARC) materials has become a challenge. In this paper, we report novel high performance BARC materials which are simultaneously capable of controlling reflectivity, planarizing on substrate surface, low bias filling without forming voids, low outgassing, high etch selectivity with resists and broad compatibility with resists. The new materials comprise of a chromophore that absorbs at 193 nm to give anti-reflective properties. By intriguing design of the crosslinking system to minimize the amount of low molecular weight additives and the by-product formation in the curing process, low-bias and low sublimation filling without formation of voids are achieved. In addition, the performance of the high etch rate BARC material can be further enhanced by blending with a low k high etch rate (~2.4X) material to achieve ultra high etch rate for ArF lithographic process. The filling properties, etch selectivity, lithographic and outgassing data of the new BARC materials will be presented.

Radiation sensitive developable bottom anti-reflective coatings (DBARC) for 193nm lithography: first generation

A first generation DBARC applicable for 1st minimum 193nm lithography is described in this paper. The polymer used in this DBARC is insoluble in the casting solvent of the resist, which is propyleneglycolmonomethyletheracetate (PGMEA). Photo acid generator (PAG) and base extractions from the DBARC coating by the resist casting solvent were examined by the DBARC dissolution rates in the developer, before and after solvent treatments. Although the resist and the DBARC do not appear to intermix, strong interaction between the two is evident by their lithographic performance and dissolution rate study.