GaPO4 sensors for gravimetric monitoring during atomic layer deposition at high temperatures

The quartz crystal microbalance is extremely useful for in situ monitoring of thin-film growth by atomic layer deposition (ALD) in a viscous flow environment. Unfortunately, conventional AT-quartz sensors are limited to growth temperatures below approximately 300 degrees C. Gallium orthophosphate (GaPO4) is an alternative piezoelectric material offering much greater high-temperature frequency stability than AT-quartz (SiO2). Our measurements reveal that the temperature coefficient for Y-11 degrees GaPO4 decreases linearly with temperature reaching 3 Hz/ degrees C at 450 degrees C. In contrast, the temperature coefficient for the SiO2 sensor increases as the cube of the sensor temperature to 650 Hz/ degrees C at 390 degrees C. To examine the effect of temperature fluctuations on the sensor frequency, we exposed the SiO2 and GaPO4 sensors to helium pulses at 400 degrees C. The resulting frequency change measured for the SiO2 sensor was approximately 40 times greater than that of the GaPO4 sensor. Next, we performed Al2O3 ALD using alternating tri-methylaluminum/water exposures at 400 degrees C and monitored the growth using the SiO2 and GaPO4 sensors. The GaPO4 sensor yielded well-defined pulse shapes in agreement with predictions, while the SiO2 pulses were severely distorted. Measurements during TiO2 ALD using alternating titanium tetrachloride/water exposures at 450 degrees C with the GaPO4 sensor also showed well-defined ALD mass steps.