Coumarin 6 (C6), a pH sensitive fluorescent molecule were doped into commercial resist systems to demonstrate a cost-effective fluorescence microscopy technique for detecting latent photoacid images in exposed chemically amplified resist films. The fluorescenec image contrast is optimized by carefully selecting optical filters to match the spectroscopic properties of C6 in the resist matrices. We demonstrate the potential of this technique for two sepcific non-invasive applications. First, a fast, conventient, fluorescence technique is demonstrated for determination of quantum yeidsl of photo-acid generation. Since the Ka of C6 in the 193nm resist system lies wihtin the range of acid concentrations that can be photogenerated, we have used this technique to evaluate the acid generation efficiency of various photo-acid generators (PAGs). The technique is based on doping the resist formulations containing the candidate PAGs with C6, coating one wafer per PAG, patterning the wafer with a dose ramp and spectroscopically imaging the wafers. The fluorescence of each pattern in the dose ramp is measured as a single image and analyzed with the optical titration model. Second, a nondestructive in-line diagnostic technique is developed for the focus calibration and validation of a projection lithography system. Our experimental results show excellent correlation between the fluorescence images and scanning electron microscope analysis of developed features. This technique has successfully been applied in both deep UV resists e.g., Shipley UVIIHS resist and 193 nm resists e.g., Shipley Vema-type resist. This method of focus calibration has also been extended to samples with feature sizes below the diffraction limit where the pitch between adjacent features is on the order of 300 nm. Image capture, data analysis, and focus latitude verification are all computer controlled from a single hardware/software platform. Typical focus calibration curves can be obtained within several minutes.
This paper reports an on-wafer photoacid determination technique that can be used to quickly screen materials that function as photoacid generators (PAGs). The technique includes adding a small amount of a pH-sensitive fluorophore into the resist and exposing the resist to x-rays. The acid generated during exposure reacts with the fluorophore and quenches the fluorescence. The efficiency of photoacid generation is evaluated by comparing the degree of fluorescence quenching. This technique is nondestructive, fast, and does not significantly change the resist chemical properties given the low concentration of the added fluorophore. Six compounds that can generate hydrogen halides as potential PAGs were evaluated using this on-wafer technique and the lithographic performance was evaluated for comparison. The commercial resist, Shipley SAL 605, is used as a reference for comparison. The result showed that TBBPA gave higher photoacid generation efficiency that TCBPA and PBP, but lower than that in SAL 605. The results of fluorescence measurements agree with the results obtained using normalized remaining thickness measurements. The advantages, however, of this fluorescence technique are that it is simple, fast, and requires fewer processing steps.
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