Negative photoresist materials for 248 nm (KrF excimer laser) implant applications are of interest to research
and development recently, due to the ever-present demand to shrink lithographically-patterned device dimensions at an
affordable cost. Challenges to developing such a successful resist are the topography of the substrate and subsequent
reflectivity complexities. Substrate reflectivity control, resist profile, and critical dimension (CD) uniformity are critical
issues that must be addressed to enable robust lithography performance at high KrF numerical aperture. The design,
synthesis and characterization of a series of polymers for negative developable bottom anti-reflective coating
(NDBARC) materials suitable for KrF negative implant resists is described.
Pitch-split resist materials have been developed for the fabrication of sub-74 nm pitch semiconductor devices. A
thermal cure method is used to enable patterning of a second layer of resist over the initially formed layer. Process
window, critical dimension uniformity, defectivity and integration with fabricator applications have been explored. A
tone inversion process has been developed to enable the application of pitch split to dark field applications in addition to
standard bright field applications.
KEYWORDS: Back end of line, Dielectrics, Etching, Lithography, Reactive ion etching, Photoresist materials, Optical lithography, Semiconducting wafers, Copper, Polishing
A novel back-end-of-line (BEOL) patterning and integration process termed Multi-Level Multiple Exposure
(MLME) technique is herein introduced. The MLME technique simplifies BEOL dual damascene (DD) integration while
simultaneously being applicable to all BEOL levels. It offers a patterning resolution reaching into the sub-100nm region
and improves semiconductor manufacturing cost and throughput. MLME employs a dual-layer imaging stack (via + trench resists) cast onto a customized etch transfer multilayer stack. This process implements a strict litho-litho-etch sequence for transferring the trench- and via-patterns into the dielectric layer. Under the MLME scheme, two imaging
steps (i.e. via- and trench-level patterning) are executed consecutively followed by a dry etch process that transfers the
lithographically-formed patterns into the customized etch transfer multilayer stack and further into the dielectric layer.
The MLME integration scheme not only decreases the number of overall process steps for the full DD BEOL process but
also eliminates several inter-tool wafer exchange sequences as performed in a conventional litho-etch-litho-etch process
flow. All MLME process steps were demonstrated i.e. combined 193nm-dry dual-resist layer MLME via- and trench-lithography,
full pattern transfer of via- and trench-patterns into the dielectric layer using reactive ion etching (RIE), as
well as electroplating and polishing of the DD patterns. This paper provides a detailed description of both post-lithography
steps of the DD process for a DD BEOL structure, i.e. (i) the RIE-pattern transfer process with the customized multilayer stack, and (ii) the metallization process completing the DD process for one BEOL layer.
Furthermore, the integration capabilities of the MLME technique were demonstrated and characterized by generating an
electrically functional via-chain connecting two neighboring BEOL layers fabricated by subsequently applying the MLME approach to both layers. An exhaustive description and evaluation of MLME lithographic patterning is given in an accompanying paper.
Lithographic scaling beyond the 22 nm node requires double patterning techniques to achieve
pitch values below 80nm. The semiconductor industry is focusing on the development of several process
techniques including track-only lithographic processing methods in order to reduce cost, cycle time and
defects. Initial efforts for track-only double expose processes have relied on the use of chemical freeze
materials to prevent inter-mixing of resists, and also by means of thermal curable materials. These two
techniques may be complementary, in the sense that a chemical freeze may be very robust for protection of
exposed regions, while thermal cure systems may provide strong protection of large unexposed areas.
We will describe our results with mainly the thermal-cure double patterning resist materials, and
the application of these materials to the fabrication of sub-80 nm pitch semiconductor structures. We will summarize the process window and defect capability of these materials, for both line/space and via applications.
KEYWORDS: Optical lithography, Einsteinium, Back end of line, Etching, Dielectrics, Semiconducting wafers, Lithography, Photoresist materials, Nanoimprint lithography, Reactive ion etching
In this work, the conventional via-first dual damascene (DD) patterning scheme is replaced by a cost-efficient
Multi-Level Multiple Exposure (MLME) patterning and etching approach. A two-layer positive-tone photoresist stack is
sequentially imaged using 193 nm dry lithography, to produce a DD resist structure that is subsequently transferred into
an auxiliary dual organic underlayer stack, and then further into a dielectric layer. This novel integration approach
eliminates inter-tool wafer exchange sequences as performed in a conventional litho-etch-litho-etch process flow, while
simultaneously being applicable to all back-end-of-the-line (BEOL) levels, ensuring throughput increase. The top and
bottom resist layers are chemically designed in such a way that they feature differential solubility in organic solvents
making it possible to coat the top photoresist onto the bottom resist layer without intermixing to enable a strict litholitho-
etch processing sequence. Independent registration of the via and trench structures in the bottom and top resist
layers is achieved by selective photospeed decoupling of the respective layers, so that the bottom resist is largely
insensitive at nominal resist exposure dose for the top resist. Imaging performance evaluation of the newly introduced
MLME technology includes the resist materials selection process and their required properties (solvent compatibility,
adhesion, photospeed, defectivity and correction of via dose bias due to trench exposure) as well as metrology work.
Image transfer of the patterned DD resist structure into an underlying transfer layer stack and then further into a
dielectric layer using Reactive Ion Etching (RIE) followed by electroplating, polishing and electrical testing was also
thoroughly investigated and is described in detail in an accompanying paper.
This work discusses the requirements and performance of Honeywell's middle layer material, UVAS, for trilayer patterning. UVAS is a high Si content polymer synthesized directly from Si containing starting monomer components. The monomers are selected to produce a film that meets the requirements as a middle layer for trilayer patterning and gives us a level of flexibility to adjust the properties of the film to meet the customer's specific photoresist and patterning requirements. Results of simulations of the substrate reflectance versus numerical aperture, UVAS thickness, and under layer film are presented. Immersion lithographic patterning of ArF photoresist line space and contact hole features will be presented. A sequence of SEM images detailing the plasma etch transfer of line space photoresist features through the middle and under layer films comprising the TLP film stack will presented. Excellent etch selectivity between the UVAS and the organic under layer film exists as no edge erosion or faceting is observed as a result of the etch process. The results of simulations of Rsub versus NA, and the thickness of each film comprising a two layer antireflective film stack will also be discussed.
Our primary platform for 157 nm positive resists is built on a copolymer of t-butyl 2-trifluoromethylacrylate (TBTFMA) and norbornene bearing hexafluoroisopropanol (NBHFA) as an acid group, which is prepared by radical copolymerization. The radical copolymerization of 2-trifluoromethylacrylic monomers with norbornene derivatives has been found through reactivity ratio determination and in situ 1H NMR analysis of kinetics to deviate from the terminal model but to follow the penultimate model. These copolymers typically contain >50 mol% TBTFMA, are lipophilic, and fail to provide good imaging due to poor wettability. Blending a homopolymer of NBHFA (optical density (OD)=1.7/micrometers at 157 nm) into the copolymers (OD=2.5-2.7/micrometers ) increases the hydrophilicity and reduces OD to 2.2-2.0/micrometers , providing high resolution images. Another platform we have identified is a copolymer of TBTFMA with vinyl ethers, which can be prepared by using a common radical initiator. Some of the vinyl ether copolymers are also homogeneously miscible with the NBHFA homopolymer and thus their OD and aqueous base development can be improved by blending.
As resist feature sizes have decreased and the performance demands on chemically amplified photoresists have increased the role of the photoacid generator (PAG) in determining overall resist performance has become increasingly apparent. Over the past 20 years a variety of different types of PAG's have been introduced as researchers have sought to optimize properties such as acid strength, acid volatility, diffusion length, wavelength response, solubility etc. PAGs that produce very strong organic acids are widely used, in part because of requirements for high photospeed resists. Most of these acid generators are based on perfluoroalkyl sulfonic acid based onium salts. In an effort to identify and characterize alternative PAGs we have investigated the performance of a variety of photoacid generators that are not based on sulfonic acids. In this report we will describe the relative reactivities of these PAGs under a variety of exposure wavelengths and processing conditions including acid diffusion proprieties and photospeed measurements.
There is currently tremendous interest in developing 157nm photoresists for imaging applications at 100nm and below. Due to the high VUV absorbance of the polymers used in 248 and 193 photoresists new materials are being investigated for applications at 157nm. In this report the characterization of a number of partially fluorinated polymers based on aromatic backbones will be described. Data on the absorbance, dissolution properties, solvent retention and acid diffusion characteristics of these systems will be presented.
Based on UV measurements at 157nm of in-house fluoropolymers we have selected (alpha) -trifluoromethylacrylate and norbornene bearing a pendant hexafluoroisopropanol group as our building blocks for 157nm resist polymers. Polymers consisting of these repeat units have an optical density/micrometers of 3 or below at 157nm. We have found that the (alpha) -trifluoromethylacrylate derivatives conveniently undergo radical copolymerization with norornenes, which has provided a breakthrough in preparation of our 157nm resist polymers. This approach offers flexibility and versatility because an acidic moiety or acid-labile group can be placed in either acrylate or norbornene repeat unit. Other platforms of interest include all acrylic, all-norbornene, and acrylic-styrenic polymers.
We have designed and developed an aqueous base soluble polymer system with a silsequioxane (SSQ) backbone for 157nm bilayer resist applications. These base resins have absorbances as low as 0.6micrometers -1 at 157nm. The imagable polymers which contain acid-labile ester functionalities have absorbances between 2.0 and 3.0micrometers -1. The silicon content of these polymers is around 15% by weight. Therefore, our polymers can be utilized in 157nm positive bilayer resist applications with a film thickness of around 150nm. We have evaluated several resist formulations based on these polymers. These resist formulations have shown high contrast and excellent resolution.
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