Techniques for directly measuring the absorbance of photoresists at EUV wavelengths

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Techniques for directly measuring the absorbance of photoresists at EUV wavelengths Manish Chandhok, a Heidi Cao, a Wang Yueh, a Eric Gullikson, b Robert Brainard, c Stewart Robertson c a Intel Corporation, Hillsboro, OR 9714 b Lawrence Berkeley National Laboratory, Berkeley CA c Shipley Company, Marlborough, MA 1 October, 003 Acknowledgements: E. Lin (NIST), G. Zhang (Intel) 1

Motivation Resist absorbance is a key parameter that can limit resolution and wall angle Calculations such as those by the CXRO website* are typically used for estimating absorbance However, there is limited validation of the calculated absorbance against measurements Experimental methods need to be investigated and a technique selected * http://cxro.lbl.gov/optical_constants

Simulated effect of reducing photoresist absorbance 3 90 0.060 Beta tool (NA=0.5, sigma=0.5) Resist thk = 60 nm, Dose =.95 mj/cm B:1 30 89 88 Resist Height (um) 0.048 0.036 0.04 0.01 B: B:3 B:4 B:5 Absorbance reducing CD (nm) 8 6 4 0 87 86 85 84 83 8 81 Angle ( ) 0.000 0.31 0.38 0.45 0.53 0.60 0.68 Distance (um) 18 EUV D 1 3 4 5 Absorbance (m -1 ) 80 Reducing absorbance increases resolution and wall angle 3

What is the target absorbance for EUVL? Beer s law states that intensity of light decreases exponentially with thickness in an absorbing media I( z) I0 exp( B z) where z = resist thickness, B = Absorbance or Dill B parameter (units: 1/m) Parameter that matters is (B z) that s been decreasing with process generation 0.7 0.6 0.5 0.4 0.3 0. 0.1 0 180 nm process 130 nm process 90 nm process EUV-D For B x z ~ 0.1, with resist thickness of 60 nm target absorbance needs to be ~ 1/m Absorbance x Resist thickness (unitless) 4

Calculating the absorbance using the CXRO website Complex refractive index n is given by n 1 i where r 0 na i x i f 1i r 0 na i x i f i n a Density MW N A r 0 = classical electron radius, = wavelength of the radiation, n a = atomic density of the material, f 1 and f are the real and imaginary parts of the atomic scattering factor that have been tabulated for various elements Model requires the following to calculate absorbance: Empirical chemical composition MW x i A i Density in gm/cm 3 Absorbance i 4 5

Procedure for validating the calculated absorbance of Shipley s EUV-D resist Calculation using CXRO website with: Density obtained by measuring the mass and the film thickness of resist spun on wafers Density obtained by Specular X-ray Reflection (SXR) measurements and elemental composition Experiment: Obtain absorbance using normal incidence reflectivity measurements Measure absorbance using grazing incidence reflectivity 6

Calculation Method 1: Estimate from CXRO Model using Weighed Density The chemical composition of EUV-D was estimated Density was determined by weighing six wafers before and after coat and using knowledge of surface area and thickness. Resulting value was 1.8 g/cm 3 Using the values for and from the CXRO website to obtain n & absorbance value at 13.5 nm n = 0.9748 Absorbance = 4.635 1/m 7

Calculation Method : Estimate from CXRO Model using SXR Density EUV-D was characterized with specular x-ray reflectivity (SXR) measurements at NIST to obtain the critical angle (Qc) and resist thickness Density can be determined from knowledge of Qc and the materials elemental composition Resulting value was 1.1497 g/cm 3 Using the values for and from the CXRO website to obtain n & absorbance value at 13.5 nm n = 0.9774 Absorbance = 4.160 1/m 8

Measurements Method 1: Grazing incidence Technique is valid provided < Fresnel equations for reflectivity The grazing incidence reflectivity at 13.5 nm of EUV-D coated on silicon was measured as a function of angle and obtained by fitting experimental data with the Fresnel equations The resulting optical parameters were: n = 0.9779 Absorbance = 4.198 1/m R p Reflectivity R s ( ) ( ) 1 0.1 0.01 1E-3 1E-4 sin( ) sin( ) (1 i ) (1 i ) (1 (1 sin( ) sin( ) i ) i ) cos ( )] cos ( )] EUV-D (=13.5 nm) 1/ 1/ 1E-5 0 0 40 60 80 (1 i ) (1 i ) Angle (deg) =0.01 =0.00451 d=14.3 nm cos ( )] cos ( )] 1/ 1/ 9

Measurements Method : Normal Incidence Reflectivity 8 Mo-Si Multi-layer (ML) wafer to get a reflective substrate for normal incidence Resist, exposure, and processing by Shipley - 100 A of EUV-D - 10 x 10 array, 1 cm square, Eo exposure pattern using 48 nm - PEB, develop Thickness remaining at each site measured Normal incidence reflectivity measured at each site Noise in data due to poor coat quality 10

Images of E 0 pattern of EUV-D resist on Mo/Si ML wafer Multilayer surface yielded poor resist coating quality Non-uniform coating increased the noise of reflectivity measurements 11

Fitting normal incidence reflectivity Vs resist thickness to obtain the absorbance Reflectivity versus thickness data was simulated for various Dill B values (n( held constant at 0.9779) using lithography simulator To reduce the impact of noise in the fit Points lying out with 3 sigma of the model are discarded Sigma value is recalculated and the process iterated until sigma stabilizes. Dill B (absorbance) value returning lowest sigma is statistically the best fit Absorbance = 4.07 1/m Reflectivity (%) Ripples occur due to standing wave in resist from index of refraction mismatch between resist and reflective substrate 70 60 50 40 30 EUV-D Reflectivity at Wavelength versus Thickness Excluded Experimental Points (more than 3 sigma from fit) Modelled Reflectivity (n = 0.9779, Dill B = 4.07 per um) Valid Experimental Points 0 0 0 40 60 80 100 10 140 EUV-D Thickness (nm) 1

Data Summary Calculation n Absorbance (1/um) Weighed method density 0.9748 4.635 SXR method density 0.9774 4.16 Measurements n Absorbance (1/um) Grazing incidence 0.9779 4.198 Normal incidence N/A 4.071 Recommended Recommended The absorbance calculated using the SXR method for the density matches the Grazing Incidence measurements within 1% 13

Discussion Density using the Weighed method is prone to error in measurement of the mass of the sample and thickness Hence, density and thus absorbance estimated by Weighed method is 10% higher than that using the SXR method which is more accurate The normal incidence measurements require a ML reflective substrate that can be expensive and may have coat quality issues The ripples in the normal incidence reflectivity measurements are modulated by real part of the index of refraction (n). But the noise observed in the experimental data is greater than the ripple amplitude and hence (n) cannot be measured this way Grazing incidence measurements are valid provided absorbance is low i.e., < Even with = 0.01, absorbance values of 10 1/m m and below can be measured using this technique which is the expected range for photoresist materials 14

Summary Calculations for estimating the absorbance are very sensitive to the assumed density values The SXR density produces calculated results very consistent with the experimental measurements made at wavelength, suggesting this is the true density and hence is the recommended density measurement technique Despite the noise in the data, the absorbance extracted from normal incidence reflectivity measurements is close (.% less) to the theoretical value The grazing incidence reflectivity measurements appear to be noise free and is simpler utilizing a bare Si wafer, rather than a Mo-Si ML wafer, and hence is the recommended absorbance measurement technique 15