A Study of Haze Generation as Thin Film Materials



Similar documents
Mask Cleaning Processes and Challenges

Techniques for removal of contamination from EUVL mask without surface damage

Conductivity of silicon can be changed several orders of magnitude by introducing impurity atoms in silicon crystal lattice.

PROVE, the next generation registration metrology tool, status report

Modification of Pd-H 2 and Pd-D 2 thin films processed by He-Ne laser

Austin Peay State University Department of Chemistry CHEM Empirical Formula of a Compound

Analysis of the Effect of Laser Bandwidth on Imaging of Memory Patterns Nakgeuon Seong a, Insung Kim b, Dongwoo Kang b, Sang-Ho Lee b, Jinphil Choi b

h e l p s y o u C O N T R O L

Lecture 30: Cleanroom design and contamination control

1. Photon Beam Damage and Charging at Solid Surfaces John H. Thomas III

Research for leachables of nuclear grade cation exchange resin

Laser sintering of greens compacts of MoSi 2

Introduction to VLSI Fabrication Technologies. Emanuele Baravelli

Total Hot Spot Management from Design Rule Definition to Silicon Fabrication

Technical Info Sheet. Ionic contamination testing in a no-clean soldering process. Scope

Fabrication of Complex Circuit Using Electrochemical Micromachining on Printed Circuit Board (PCB)

Chemical Calculations: The Mole Concept and Chemical Formulas. AW Atomic weight (mass of the atom of an element) was determined by relative weights.

High quality mask storage in an Advanced Logic-Fab

Supporting Online Material for

Supporting Information

Mass production, R&D Failure analysis. Fault site pin-pointing (EM, OBIRCH, FIB, etc. ) Bottleneck Physical science analysis (SEM, TEM, Auger, etc.

SEM Analysis of CO 2 Laser Treated Cotton Grey Fabric

Implementation Of High-k/Metal Gates In High-Volume Manufacturing

Nanometer-scale imaging and metrology, nano-fabrication with the Orion Helium Ion Microscope

Contamination. Cleanroom. Cleanroom for micro and nano fabrication. Particle Contamination and Yield in Semiconductors.

Laser beam sintering of coatings and structures

1. INTRODUCTION ABSTRACT

Chapter 1: Moles and equations. Learning outcomes. you should be able to:

Measurement results on after etch resist coated features on the new Leica Microsystems LWM270 DUV critical dimension metrology system

Coating Technology: Evaporation Vs Sputtering

QUALANOD SPECIFICATIONS UPDATE SHEET Nº 9 Edition page 1/5 COLD SEALING PROCESS

Develop a Quantitative Analytical Method for low (» 1 ppm) levels of Sulfate

New 3-Dimensional AFM for CD Measurement and Sidewall Characterization

Study of tungsten oxidation in O 2 /H 2 /N 2 downstream plasma

Improved Contact Formation for Large Area Solar Cells Using the Alternative Seed Layer (ASL) Process

Good Boards = Results

Physical & Chemical Properties. Properties

Supporting information

Aging of Zeolite SCR Catalysts

DATA SHEET PART NO. : L-314YD REV : A / 4

Effect of surface area, pore volume and particle size of P25 titania on the phase transformation of anatase to rutile

BIOACTIVE COATINGS ON 316L STAINLESS STEEL IMPLANTS

Salt Weathering of Masonry Walls The Venice Experience. By M. Collepardi, S. Collepardi and R. Troli

Photomask SBU: 65nm Dry Etch has Arrived! Michael D. Archuletta Dr. Chris Constantine Dr. Dave Johnson

Preparation of ZnS and SnS Nanopowders by Modified SILAR Technique

Adhesive Bonding of Natural Stone

OPTIMIZING OF THERMAL EVAPORATION PROCESS COMPARED TO MAGNETRON SPUTTERING FOR FABRICATION OF TITANIA QUANTUM DOTS

STM, LEED and Mass spectrometry

Usage of Carbon Nanotubes in Scanning Probe Microscopes as Probe. Keywords: Carbon Nanotube, Scanning Probe Microscope

Electron Beam and Sputter Deposition Choosing Process Parameters

Development of High-Speed High-Precision Cooling Plate

Photolithography (source: Wikipedia)

EXPERIMENT 5. Molecular Absorption Spectroscopy: Determination of Iron With 1,10-Phenanthroline

Nickel Free Room Temperature Seal: an innovative and ecological process

Utilization of AIMS Bossung plots to predict Qz height deviations from nominal

Demonstration of sub-4 nm nanoimprint lithography using a template fabricated by helium ion beam lithography

WHAT IS IN FERTILIZER OTHER THAN NUTRIENTS?

THE USE OF OZONATED HF SOLUTIONS FOR POLYSILICON STRIPPING

KALPANA INDUSTRIES LTD. TECHNICAL DATA SHEET

Effect of Dissolved CO 2 in De-ionized Water in Reducing Wafer Damage During Megasonic Cleaning in MegPie. Arizona 85721, USA. Arizona 85721, USA

Dimethylglyoxime Method Method to 6.0 mg/l Ni TNTplus 856

atm = 760 torr = 760 mm Hg = kpa = psi. = atm. = atm. = 107 kpa 760 torr 1 atm 760 mm Hg = 790.

Chem 1A Exam 2 Review Problems

Effect of Magnesium Oxide Content on Final Slag Fluidity of Blast Furnace

What is optical lithography? The optical system Production process Future and limits of optical lithography References. Optical lithography

Scanning Electron Microscopy Services for Pharmaceutical Manufacturers

Influence of CO2 Bubbling (Carbonation) During Semiconductor Wafer Sawing Process. KP Yan, Reinhold Gaertner, KK Ng

Miniaturizing Flexible Circuits for use in Medical Electronics. Nate Kreutter 3M

Corning HPFS 7979, 7980, 8655 Fused Silica. Optical Materials Product Information Specialty Materials Division

Vacuum Pumping of Large Vessels and Modelling of Extended UHV Systems

Name Date Class CHAPTER 1 REVIEW. Answer the following questions in the space provided.

MICROPOSIT LOL 1000 AND 2000 LIFTOFF LAYERS For Microlithography Applications

EUV lithography NXE platform performance overview

Lecture 12. Physical Vapor Deposition: Evaporation and Sputtering Reading: Chapter 12. ECE Dr. Alan Doolittle

Ultra line narrowed injection lock laser light source for higher NA ArF immersion lithography tool

the runnerless types of molds are explained post molding operations are described the basic methods of applied decoration methods are examined

Vacuum Evaporation Recap

Stainless Steel Marking Guide

Introduction to microstructure

AORC Technical meeting 2014

... complement Information for Processing

Hardness ions also interfere with many chemical processes such as chemical compounding and aqueous cleaners.

Phosphate Recovery from Municipal Wastewater through Crystallization of Calcium Phosphate

The study of structural and optical properties of TiO 2 :Tb thin films

Designing and Manufacturing Femtoseconds Ultra-broadband Lasers: Proven, Hands-free Reliability

Defect studies of optical materials using near-field scanning optical microscopy and spectroscopy

To meet the requirements of demanding new

SCENIC VIEW SV 10 SECTION SOLAR CONTROL FILMS

LEAD CRYSTAL. User Manual. Valve-regulated lead-crystal batteries Energy storage Cells

EXPERIMENT 7 Reaction Stoichiometry and Percent Yield

Micro-Power Generation

Chapter 6. Photolithography 2005/10/18 1

Table 1. Common esters used for flavors and fragrances

Additional evidence of EUV blank defects first seen by wafer printing

Types of Epitaxy. Homoepitaxy. Heteroepitaxy

MOLES AND MOLE CALCULATIONS

Wastewater Reuse. Typical treated wastewater is:

MISCIBILITY AND INTERACTIONS IN CHITOSAN AND POLYACRYLAMIDE MIXTURES

Quartz Glass. Tubes and Rods

Transcription:

A Study of Haze Generation as Thin Film Materials Ju-Hyun Kang, Han-Sun Cha*, Sin-Ju Yang, Chul-Kyu Yang, Jin-Ho Ahn*, Kee-Soo Nam, Jong-Min Kim**, Manish Patil**, Ik-Bum Hur** and Sang-Soo Choi** Blank Mask R&D Center, S&S TECH CORPORATION 9, Horim-Dong, Dalseo-Gu, Daegu-City, 704-240, Korea * Division of Advanced Materials Science Engineering, Hanyang University 17, Haengdang-Dong, Seongdong-Gu, Seoul-City, 133-791, Korea ** R&D Center, Photronics-PKL 493-3, Sungsung-Dong, Cheonan-City, Choongnam-Do, 330-300, Korea Phone: +82-53-589-1669 Fax: +82-53-585-7170 e-mail: jhkang@snstech.co.kr ABSTRACT For high quality products in the semiconductor and photomask industries, exposure wavelength has been shortening from i-line to ArF to embody the high resolution as critical dimension (CD) shrinkage and the specifications have been restricted. However, a new defect issue called haze has appeared that is shortening the wavelength. This defect is caused by the photoreaction of chemical residues exposed to SO 4 2-, NH 4 + and other chemicals. Accordingly, in this paper we investigated the generation of haze in thin film materials. For fabrication of various thin films, the materials which were metal, compound material without nitrogen, and compound material with nitrogen, were deposited on a quartz substrate using sputtering. Then, we chemically treated the thin film materials using various conditions including sulfuric peroxide mixture (SPM) and standard cleaning (SC-1). First, the concentration of ions on the thin film materials was measured using ion chromatography (IC) analysis. Second, haze defects were inspected after exposure in order to evaluate the difference in haze generation on the thin film materials. Also, we investigated the numbers and shape of the occurrences of haze. Keywords: haze, ion chromatography, thin film material, exposure, SO 4 2-, NH 4 + 1. INTRODUCTION The critical dimension (CD) has been minimized and the exposure wavelength has been shortened to embody the higher integration and larger capacity of semiconductors. However, exposure energy has been increasing as the exposure wavelength shortening, and this causes the issue called haze. This defect is caused by the exposure of high energy on the photomask surface, and reduces the lifetime of the photomask, so this defect eventually decreases productivity in the lithography. Accordingly, the haze issue must be overcome to improve productivity. As shown in previous reports, the residual ions SOx, NOx and NH 4 adhered to the photomask surface during the cleaning process, and these caused a photoreaction due to exposure to high energy. Therefore, the haze defect was caused by photoreaction. From the result of these reports, it was shown that the haze was also generated by outgassed contaminants from pellicle materials such as frames, films, adhesives and other materials. However, most of the studies focused on the photomask process. Accordingly, we investigated haze generation on the mask blanks of thin film materials. Photomask Technology 2007, edited by Robert J. Naber, Hiroichi Kawahira Proc. of SPIE Vol. 6730, 67304K, (2007) 0277-786X/07/$18 doi: 10.1117/12.746684 Proc. of SPIE Vol. 6730 67304K-1

2. EXPERIMENTAL 2.1 Process Flow Ion Extraction Treatment by Quartz Container with DI Water IC Analysis Thin Film by Sputtering Chemical Treatment as Conditions 1 st Exposure with 7, 10 kj Haze Inspection 2nd Exposure with 5 kj Haze Inspection Figure. 1 Process Flow We studied the generation of haze on thin film materials in figure 1. Figure 1 shows the process flow of this study. As shown in figure 1, thin films were deposited using the sputtering system and treated with various chemical conditions. And then, the adsorbed ion concentration on the surface was analyzed using IC analysis. Also we inspected the number and shape of occurrence of haze by microscope after ArF laser acceleration. 2.2 Thin Film Condition In this paper, we prepared the three categories of material such as pure metal, compound materials without nitrogen and compound materials with nitrogen as shown in table 1. Materials A ~ D were pure metals, and materials E and F which are phase shift mask (PSM) materials were compound materials without nitrogen. Materials G and H were compound materials based on material E with nitrogen, and material G had a relatively higher composition of nitrogen than material H. Finally, materials I and J were compound materials based on material F with nitrogen, and material I had a relatively higher composition of nitrogen than material J. Materials G ~ J were also PSM materials. Table 1. Types of Samples Pure Metal Compound Material without Nitrogen Compound Material with Nitrogen Materials A, B, C, D E F G, H (Material E based) I, J (Material F based) We chemically treated the materials with various conditions as shown in table 2 for thin film materials. Condition 1 did not apply SPM or SC-1, and condition 2 applied only SPM for 10 minutes using the dipping method. Condition 3 applied both SPM and SC-1 for 10 minutes using the dipping method. After treatment, the thin film materials with chemical treatment were kept in shipping boxes. Table 2. Chemical Treatment as Conditions Conditions SPM SC 1 1 No Dipping No Dipping 2 Dipping for 10 min No Dipping 3 Dipping for 10 min Dipping for 10 min Proc. of SPIE Vol. 6730 67304K-2

2.3 IC Analysis Condition We measured the ion concentrations of the thin films material using IC analysis. First, we extracted ions with deionized (DI) water using a quartz container as shown in figure 2. Gasket Cover Teflon bolt 6 Inch Quartz Quartz Figure. 2 Quartz Container for Ion Extraction Figure 2 shows the quartz container for ion extraction. Quartz was selected as the container material to minimize the impurities from the container and to prevent re-adsorption of the impurities. Gasket and teflon bolt were used to seal the container. The ion extraction progressed through heat treatment in the DI water. The IC analysis was done using a DIONEX-320 series from the ion extracted DI water. 2.4 ArF Laser Acceleration Condition ArF laser acceleration was applied for haze generation as in the conditions of table 3. After ArF laser acceleration, we inspected the surface of the thin film materials using microscopy. Table 3. Conditions of ArF Laser Acceleration Items Energy Source Beam Size on Sample Energy Fluency Condition 193 mm 5 mm x 5 mm 150 Hz Humidity 45 % Temperature 23 Air Flow 0.5 LPM Proc. of SPIE Vol. 6730 67304K-3

3. RESULTS AND DISCUSSION 3.1. IC Analysis Results IC analysis progressed for thin film materials. Table 4 shows the results of the IC analysis for condition 1, which did not apply. Despite no chemical treatment for the thin film materials, ions were detected for all thin film materials, because ions were generated form the shipping box and environmental condition such as cleanroom. There was also a slight difference in ion concentrations for all the materials. As shown in table 4, F -, Cl -, SO 2-4 and NH + 4 ions were detected for all of the thin film materials. The total ion concentration for all of the thin film materials was from 4 ppbv to 7 ppbv. Table 4. Ion Analysis Results of Condition 1 by IC (unit : ppbv) Materials Description F - Cl - 2- + SO 4 NH 4 Total Material A Pure Metal 0.33 0.64 1.54 1.63 4.14 Material B Pure Metal 0.34 0.54 1.31 1.48 3.67 Material C Pure Metal 0.35 0.58 1.51 1.43 3.87 Material D Pure Metal 0.48 0.64 1.74 1.49 4.35 Material E Compound Material without Nitrogen 0.33 1.04 2.34 2.47 6.18 Material F Compound Material without Nitrogen 0.45 1.21 2.12 2.07 5.85 Material G Compound Material with Nitrogen 0.66 1.26 2.99 2.46 7.37 Material H Compound Material with Nitrogen 0.59 1.06 2.59 2.52 6.72 Material I Compound Material with Nitrogen 0.62 1.2 2.22 2.34 6.38 Material J Compound Material with Nitrogen 0.57 1.18 2.11 2.17 6.03 NO 3, Na, K, Mg, Ca ions were not defected. Table 5 shows the results of the IC analysis for condition 2, which was treated only with SPM. More SO 4 2- ions were detected compared to condition 1. First, in the case of materials A ~ D, which were the pure metals, around 5 ppbv ion concentrations were analyzed from materials A ~ C, but material D generated 20 ppbv, which was 4 times higher than the other materials. This difference in ion concentration occurred due to diversion of the ion adsorption rate of the materials. For material E, which was PSM material without nitrogen, 20.26 ppbv of SO 4 2- was deteced and material F had 9.45 ppbv, so the ion concentrations in material E was 1.2 times higher than material F s concentration, and the difference of the ion adsorption rate was caused by the different composition of the transition metal. For PSM material G and H without nitrogen, which were based on material E, the difference in the total ion concentration between materials G and H was 26 ppbv. The highest concentration of SO 4 2- ion was detected in material G. Therefore, we could find that the difference of ion concentration was due to nitrogen composition in materials G and H. Also in the PSM materials I and J with nitrogen, which were based on material F, the total ion concentration of material I, with a high composition of nitrogen, was 50.64 ppbv, and this concentration was higher than material J s concentration, with a low composition of nitrogen. This tendency was similar to materials G and H. However, the difference in the ion concentrations due to nitrogen composition was as small as 6 ppbv. There was twice as much ion concentration among PSM materials in materials G ~ H, and this difference due to a mother material difference. Due to the results of the IC analysis of the thin film materials, we could conclude that the difference in the ion concentration of the thin film materials was caused by a variation in the ion adsorption rate that occurred due to the different surface energy state of the material types and their compositions. Also the concentrations of F -, Cl - and NH 4 + ions increased compared to condition 1 because of impurities in the SPM solution. Therefore, selection of SPM solution is needed. We rinsed after the SPM treatment for 10 minutes, but SO 4 2- ions were detected. Accordingly, more rinse time is needed to remove SO 4 2- ions, which also have a sticky characteristic in cleaning process. Proc. of SPIE Vol. 6730 67304K-4

Table 5. Ion Analysis Results of Condition 2 by IC (unit : ppbv) Materials Description F - Cl - 2- SO 4 + NH 4 Total Material A Pure Metal 9.25 7.55 5.95 2.16 24.91 Material B Pure Metal 8.21 6.25 4.78 2.14 21.38 Material C Pure Metal 7.52 6.01 5.12 4.01 22.66 Material D Pure Metal 9.56 7.85 20.54 12.54 50.49 Material E Compound Material without Nitrogen 6.58 6.01 20.26 9.57 42.42 Material F Compound Material without Nitrogen 6.32 5.57 9.45 6.95 28.29 Material G Compound Material with Nitrogen 11.93 10.94 39.65 20.22 82.74 Material H Compound Material with Nitrogen 7.16 9.32 25.54 14.55 56.57 Material I Compound Material with Nitrogen 6.76 9.01 22.32 12.55 50.64 Material J Compound Material with Nitrogen 4.77 6.37 21.45 10.54 44.13 Table 6 shows the results of the IC analysis for condition 3, which was treated with both SPM and SC-1. Concentrations of NH + 4 ions increased. First, in the case of materials A ~ D, which were pure metals, around 25 ppbv of NH + 4 ion concentration was analyzed from materials A ~ C, but material D generated 90 ppbv, which was about 4 times higher than the other materials. Material E, which was PSM material without nitrogen, showed 96.17 ppbv of NH + 4, and material F was analyzed to be 26.63 ppbv. This concentration was 4 times higher than material F s concentration. For PSM material G and H without nitrogen, which were based on material E, the total ion concentration of material G was 227.47 ppbv, which was about 2 times higher than material H`s concentration. The highest concentration of NH + 4 ions was detected from material G. On the other hand, the total ion concentration and NH + 4 of material H was 121.25 ppbv and 57.02 ppbv, and this concentration were lower than material G. Therefore, we could find the same tendency that ion concentrations are different due to the composition ratio of nitrogen in the case of materials G and H. Also, for PSM materials I and J with nitrogen, which were based on material F, the total ion concentration of Material I was higher than material J, where material I s concentration was 84.65 ppbv. TheNH + 4 ion concentration of materials I and J were 31.57 ppbv and 20.2 ppbv, respectively. However, the difference in the total ion concentration between materials I and J was small, only 18 ppbv. Table 6. Ion Analysis Results of Condition 3 by IC (unit : ppbv) Materials Description F - Cl - 2- + SO 4 NH 4 Total Material A Pure Metal 17.03 15.33 23.59 26.22 82.17 Material B Pure Metal 16.93 14.57 22.25 25.36 79.11 Material C Pure Metal 16.53 15.25 21.46 20.2 73.44 Material D Pure Metal 24.54 28.67 25.82 90.18 169.21 Material E Compound Material without Nitrogen 14.54 21.4 25.75 96.17 157.86 Material F Compound Material without Nitrogen 11.76 13.89 23.42 26.63 75.7 Material G Compound Material with Nitrogen 15.34 19.22 42.65 150.26 227.47 Material H Compound Material with Nitrogen 14.94 18.67 30.62 57.02 121.25 Material I Compound Material with Nitrogen 15.34 11.15 26.59 31.57 84.65 Material J Compound Material with Nitrogen 14.53 10.12 22.12 20.2 66.97 Proc. of SPIE Vol. 6730 67304K-5

As shown in the results of the IC analysis of these conditions, the pure metal materials such as A ~ C had a relatively low total ion concentration compared to materials D ~ J. For PSM materials E and F without nitrogen, the total ion concentration of these materials was high compared to those of the pure metal materials and was low compared to those of the PSM materials with nitrogen, because the ion adsorption rate was different for the PSM material composition, and we could find that total the ion concentration was determined as a composition ratio of nitrogen. Therefore, types and composition of the materials and nitrogen composition were the dominant factors for low ion concentrations in the selection of materials for binary and PSM as the mask blanks. 3.2. Haze Generation as ArF Acceleration Results 3.2.1 Counts of Haze Defects We did ArF laser acceleration to generate the haze and count the number of occurrences of haze. In the case of condition 1, the energy of the ArF laser acceleration was 10 kj due to no chemical treatment and the energy of the ArF laser acceleration was 7 kj in conditions 2 and 3 due to chemical treatment. An additional ArF laser acceleration was done using an additional 5 kj to investigate the haze generation from exposure energy. In condition 1, no haze defect was found at 10 kj and 15 kj of exposure energy, because the concentration of ions, such as SO 4 2- and NH 4 +, was very low. 50-250 4Q 7kJ PiLls 5 kj a Sulfate a Total Ion 15 mm Spot Area 5 mm 5 mm 5 mm 30 a 15 mm = 0 I- C 20 100 C0 1) n 10 0- - 4iø-; /1 I I I I I I A B C D E F G H I J -- Pure Metal Compound Material Compound Material without Nitrogen with Nitrogen Figure. 3 Haze Defect Count Results by ArF Laer Acceleration of Condition 2 Figure 3 shows the haze inspection results of condition 2. The haze inspection area was 15 mm x 15 mm around a spot area of 5 mm x 5 mm as shown in figure 3. For pure metal materials A ~ D, number of occurrence of the haze defect in the pure metal materials A ~ C, which had low ion concentrations of about 25 ppbv, was under 3 EA/cm2, and in material D, which had high ion concentrations of 50 ppbv, the number of occurrence of the haze defect was 15 EA/cm2. The Proc. of SPIE Vol. 6730 67304K-6

2- variations of total ion concentrations were twice as large, SO 4 ion concentrations were 4 times as large, and the difference in the number of haze defects was 5 times as large between materials A ~ C and material D. Therefore, we could find that relationship between the number of haze defects and the SO 2-4 ion concentration was in direct proportion. For PSM materials E and F without nitrogen, the number of haze defects in material E was 10 EA/cm2, and material F s number of haze defect was 5 EA/cm2, so material E s haze numbers were twice that of material F. The concentration of the total ions and SO 2-4 ion concentrations in material E were 42 ppbv and 20.26 ppbv, and for material F were 28.29 ppbv and 9.45 ppbv, respectively. Therefore, the relationship between SO 2-4 ion concentrations and haze defects was in direct proportion in the case of PSM materials E and F. For PSM materials G and H with nitrogen, which were based on material E, 22.9 EA/cm2 of haze defects was generated in material G and 12.4 EA/cm2 in material H. The number of haze defects in material G was 1.5 times higher than material H. The concentration of total ions and SO 2-4 ion was 82.74 ppbv and 39.65 ppbv in material G, and 56.57 2- ppbv and 25.54 ppbv in material H. SO 4 ion concentration in material G were 1.5 times higher than material H. Accordingly, the variation of total ion concentration was almost the same as the difference of haze defects in materials G and H. We could find that the relationship between the haze defect and the total ion concentration was in direct proportion here, too. For PSM materials I and J with nitrogen, which were based on material F, 8.5 EA/cm2 of haze defects were generated in material I and 7.1 EA/cm2 in material J. For the ion concentration in Materials I and J, the concentrations of total ions and SO 2-4 were 50.64 ppbv and 22.32 ppbv for material I, and that of material J were 44.13 ppbv and 21.45 ppbv, respectively. The variation of ion concentrations and the difference in the haze defects between material I and J were small. In accordance with above results, we could identify that the concentration of total ions and the SO 2-4 ions was a very important factor in the generation of haze defects. 50 40 c' 30 C, 7 kj -, Plus 5 kj Ammonia Total Ion Uncountable r Uncountable Uncountable 15 mm Spot Area 5 mm 5 mm 5 mm 15 mm 250 200 C 20 10.U 0 A B C D E F G H I J 0 Pure Metal Compound Material without Nitrogen Figure. 4 Results of Haze Acceleration Test as condition 3 Compound Material with Nitrogen Proc. of SPIE Vol. 6730 67304K-7

Figure 4 shows the haze inspection results for condition 3. For the pure metal materials A ~ D, the number of haze defects in pure metal materials A ~ C with ion concentrations of about 80 ppbv was small, at just 17 EA/cm2, when compare to material D with ion concentrations of 170 ppbv at 12 kj. The number of haze defects of material D was uncountable at 12 kj. The total ion concentration in materials A ~ C was twice that of material D, and the NH + 4 ion concentrations were 4 times that of material D. Therefore, the difference in the haze defects in materials A ~ D was caused by the different concentrations of total ions and NH + 4 ions. NH + 4 ion concentrations were an important factor for haze generation in condition 3. That is, number of haze defects increased as the NH + 4 ion concentration increased. For PSM materials E and F without nitrogen, the number of haze defects in material E was uncountable, and 10 EA/cm2 of haze defects were generated in material H. The concentration of total ions and the NH + 4 ions in material E were 157.86 ppbv and 96.17 ppbv, and these of material F were 75.7 ppbv and 26.63 ppbv, respectively. Accordingly, the number of haze defects increased with the NH + 4 ion concentration in materials E and F. This tendency was the same in materials A ~ D. For PSM materials G and H with nitrogen, which were based on material E, uncountable haze defects was generated in + material G and haze defects of 25.8 EA/cm2 was generated in material H. The concentration of total ions and the NH 4 ions in material G were higher than material H at 227.47 ppbv and 150.26 ppbv. Accordingly, the number of haze defects rapidly rose with concentration of total ions and the NH + 4 ions. This was the same for the results of the pure metal materials and material E and F, above. For PSM materials I and J with nitrogen, which were based on material F, haze defects of 16.9 EA/cm2 was counted in material I, twice that of material J, and haze defects of 8.5 EA/cm2 were generated in material J. The ion concentrations and number of haze defects were twice that of material J. As a result, the relationship between ion concentrations and the number of haze defects was in direct proportion for materials I and J. In accordance with the results of the haze inspection of the conditions, the number of haze defects increased as the ion concentration increased. We confirmed that ions such as SO 2-4 and NH + 4 were especially important factors in the generation of haze defects. 3.2.2 Shape Investigation of Haze Defects The shape of the haze defects was analyzed with respect to the materials and conditions in this paper. At the same time, the change of shape was analyzed with respect to the exposure energy. First, we could not find a difference due to the condition in the shape of the haze defects in the pure metals. The shape was circle type. Circle Haze Circle Haze a 1- Lens Contamination 100 Lens Contamination Figure. 5 Representative Haze Defect Images of Material A ~ D Figure 5 shows a representative haze defect images of materials A ~ D. As shown in figure 5, the generated haze defects in the pure metal materials has the shape of circle, and the size of the haze defect was slightly different, because the concentrations of SO 4 2- and NH 4 + ions and the surface state of the materials was almost the same due to the same Proc. of SPIE Vol. 6730 67304K-8

material group of the metals. The ion concentration of material D was higher than the other pure metal materials, but the shape of the haze defects was circle type. Only material D has many number of haze defect. PSM materials E and F without nitrogen had circle type haze defects, and they were similar to those of the pure metal materials. Circle Haze Circle Haze Lens Contamination (a) Material E (b) Material F Fig. 6 Representative Haze Defect Images of Material E, F Figure 5 shows the representative haze defect images of materials E and F. As shown in figure 6, the haze defects in materials E and F were circle type haze with varying size. Oval 0Haze Spot Group Haze t Flower Haze (a) Material G 00 (b) Material H Distorted Circle Haze (c) Material I (d) Material J Figure. 7 Representative Haze Defect Images of Material G ~ J Proc. of SPIE Vol. 6730 67304K-9

Figure 7 shows a representative haze defect images of materials G ~ H with nitrogen. The type of haze defect in materials G and H was like oval shaped as in fig 7 (a), or spot group shaped as in figure 7 (b). The type of haze defects in materials I and J were different compared to material G and H as shown in figure 7 (c) and (d). In accordance with the results of the inspection of haze type, the types of haze in pure metal materials and PSM materials without nitrogen in materials A ~ F were a similar circle type haze defects, but the types of haze in the PSM materials with nitrogen in materials G ~ J were different than material A ~ F. The ion concentrations of materials G ~ J were higher than the other materials, and haze generation was more unstable as the haze occurrence rate increased because the ion concentration was higher. Next, the shape of the haze was analyzed after 5 kj of ArF laser acceleration was added to each material. 7 kj + 5 kj Just Size Increased 3.5 EA/cm2 5.1 EA/cm2 Figure. 8 Representative Haze defect Images of Material A ~ D as Exposure Energy Figure 8 shows the representative haze defect images of materials A ~ D after 5 kj ArF laser acceleration was added. As shown in figure 8, there was no difference in the shape of the haze defect, but the size became bigger. We could confirm the same results in the other pure metal materials. 7 kj + 5 kj Just Size Incressed (b) 21.9 EA/cm2 Uncountable Figure. 9 Representative Haze defect Images of Material E, F as Exposure Energy Figure 9 shows representative haze defect images of PSM materials E and F after 5 kj ArF laser acceleration was added. As shown in figure 9, there was no difference in the shape of the haze but the size and number of haze defects increased. Proc. of SPIE Vol. 6730 67304K-10

7 kj + 5 kj 4j7 p ;-_. The shape of Haze Defect changed '- t cc. 'I -' -? ij Growth 'k. I rt X50 20 (a) Material G 7 kj + 5 kj The Size and Shape of Haze Defect Changed Nucleation of Haze (b) Material H.. The Size and Shape of Haze Defect Changed 7 kj + 5 kj S 0 lao I Ice (c) Material I 7 kj + 5 kj The Size and Shape of Haze Defect Changed (d) Material J Figure. 10 Representative Haze defect Images of Material G ~ J as Exposure Energy Proc. of SPIE Vol. 6730 67304K-11

Figure 10 shows the representative haze defect images of PSM materials G ~ J after 5 kj of ArF laser acceleration was added. As shown in figure 10, the shape and size of the haze defect changed. For material G, the shape of the haze defect was circle type haze early on, but the shape of the haze defect changed to a branch type haze and the size increased as 5 kj ArF laser acceleration was added. Additionally, large number of haze defects was generated. For material H, a large numbers of nucleations were generated as the ArF laser acceleration was increased. There was also changing of shape and increasing size in the haze defects in materials I and J. In materials G and H, which were based on material E, and in material I and J, which were based on material F, there was a different changing of shape, because the surface energy was different then the composition of the transition metal in the mother materials. In accordance with the results of the haze defect shape inspection, pure metal materials A ~ D and PSM materials E and F without nitrogen had circle type haze in the initial exposure, and there was no difference in the shape of the haze as exposure energy was increased. Only the size of haze defects was increased with increasing exposure energy. PSM materials G ~ H with nitrogen had a different type of haze defect in each material in the initial exposure, and the shape of the haze defects changed as exposure energy was increased. The shape change and size and number increase in material G were much larger than materials H ~ J, because the instability of the haze generation increased especially due to differences in the composition and adsorbed ion concentrations. 4. CONCLUSION As a result, we could confirm that the adsorbed ion concentration on the surface was different in the thin film materials, because the materials have different surface energy due to composition: the composition of the transition metals and the composition ratio of nitrogen. Therefore, the number and shape of the haze defects were different after the ArF laser acceleration. Also, PSM materials with and without nitrogen have unstable characteristics in their haze generation compared to the pure metal materials, and PSM materials without nitrogen were more stable than PSM materials with nitrogen for haze generation. Accordingly, it is very important to select a thin film material to reduce the haze defect. We need more research to investigate the mechanism of haze generation in the thin film materials. 5. ACKNOWLEDGEMENTS This work was supported by Research and Development (2007. May ~ 2009. Apr) project of Small and Medium Business Administration. REFERENCE 1. H. B. Kang et al., A study for the control of chemical residuals on photomask by using a thermal treatment for 65-nm node, Proc. SPIE, vol. 5853, 2005, 501-528 2. F. Eschbach et al., Photomask lifetime issues in ArF lithography, Proc. SPIE, vol. 5853, 2005, 74-82 3. K. Bhattacharyya et al., An Investigation of a New Generation of Progressive Mask Defects on Pattern Side of Advanced Photomasks, Proc. SPIE, vol. 5853, 2005, 100-108 4. F. Eschbach et al., ArF lithography reticle crystal growth contributing factors, Proc. SPIE, vol. 5567, 2004, 497-505 5. S. J. Han et at., The Study on Characteristics and Control of Haze Contamination induced by Photochemical Reaction, Proc. SPIE, vol. 5130, 2003, 563-567 Proc. of SPIE Vol. 6730 67304K-12