Non-Contact C-V Technique for high-k Applications. Piotr Edelman, Alexandre Savtchouk, Marshall Wilson, John D' Amico, Joseph N. Kochey, Dmitriy Marinskiy, and Jacek Lagowski Semiconductor Diagnostics, Inc.; 3650 Spectrum Blvd. Ste. 130; Tampa, FL 33612 USA Abstract. This non-contact high-k monitoring technique is based on a differential quasistatic C-V that is generated using timeresolved metrology combining corona charging and contact potential difference (CPD) measurements. The technique incorporates transconductance corrections that enable measurements in the high field range (lOMV/cm) required for extraction of large dielectric capacitance corresponding to ultra-low equivalent electrical oxide thickness (EOT) down to the sub-nanometer range. It also provides a means for monitoring the flat band voltage, VFB, the interface trap spectra, DIT, and the total dielectric charge, dQTOT- This technique is seen as a replacement for not only MOS C-V measurements but also for mercury-probe C-V. EOT measurement by the differential corona C-V has a major advantage over optical methods because it is not affected by water adsorption and molecular airborne contamination, MAC. These effects have been a problem for optical metrology of ultra-thin dielectrics. The presented results illustrate the application of the technique to state of the art gate dielectrics, including Si-O-N and HfO2. surface voltage caused by the corona charge dQc on the dielectric surface. INTRODUCTION A great deal of effort has been recently devoted to improving non-contact corona metrology for electrical monitoring of dielectrics on silicon wafers. This technique involves charging a dielectric surface with ions created by a corona discharge in air and measuring of the surface potential with a vibrating capacitive electrode [1,2]. No need for preparation of any test structures results in cost and time saving advantages over the commonly used MOS C-V technique. The very fast feedback of results to processing has been a driving force for implementation of non-contact metrology on silicon microelectronic fabrication lines. Fast data feedback is especially important for research and development, R&D. Most recently, the interest in corona metrology has increased further due to R&D on new ultra-thin gate dielectrics and the realization that monitoring of these films cannot be done solely through optical technology [3]. Hydrocarbon deposits from molecular airborne contamination and water adsorbed from moisture in the ambient create a layer of surface contamination that artificially increases optical thickness, making it difficult to determine the correct thickness of a dielectric underlayer. In corona metrology the contamination layer behaves as an electrical dipole layer covering the dielectric. It shifts the voltage scale by AV^ie, but does not alter the electrical thickness of the dielectric obtained from capacitance C = dQc/dV, where dV is the change of CORONA C-V MEASUREMENT Electrical monitoring of ultra-thin dielectrics requires overcoming two fundamental difficulties that would be encountered in any C-V technique. First, the measurement must be performed in the presence of substantial leakage current flowing across a dielectric [4,5]. This is a consequence of direct tunneling promoted by the ultra-low thickness. Second, dielectric capacitance must be extracted from total capacitance using high-field data in order to reduce the substrate space charge contribution to capacitance [6,7]. This further enhances the interference from leakage. In this respect corona metrology has a significant advantage over MOS-CV, namely, direct tunneling currents are orders of magnitude lower than that in MOS capacitors for the same dielectric field [4]. The electrical equivalent oxide thickness eEOT, or simply EOT, is the key output parameter of a C-V measurement. It is defined as the electrical thickness of SiO2 that gives a capacitance the same as the dielectric capacitance, Cd. Accordingly, or (La) (l.b) CP683, Characterization and Metrology for VLSI Technology: 2003 International Conference, edited by D. G. Seiler, A. C. Diebold, T. J. Shaffner, R. McDonald, S. Zollner, R. P. Khosla, and E. M. Secula © 2003 American Institute of Physics 0-7354-0152-7/03/$20.00 160 FLASK ANALOGY OF C-V EOT MEASUREMENT where s0 is the permittivity of free space, Td is the thickness of a dielectric, and KSio2 and K are the dielectric constants of SiO2 and of the measured dielectric, respectively. The corona C-V metrology is an extension of the technique for measuring dielectric leakage current [5] and the self-adjusting steady state method referred to as SASS Tox [4]. However, in contrast to the single large charge pulse used in these measurements, the corona C-V uses a series of very quick charging with a small dose, dQc. Each charging is followed by very precise time resolved monitoring of the contact potential with a time constant of 10ms and a sensitivity of 0.1 mV. The latter enables the required precision in small differential voltage measurement, dV. To achieve the necessary corona charging precision, one must precisely control several corona parameters, namely; the discharge current value, the deposition time, the corona gun geometry, its distance to the dielectric, and a dynamic vacuum controlling the ambient within the corona gun assembly. For very precise measurements, a feedback between measured voltage and the corona gun compensates for deposition rate changes caused by electrostatic forces between ions approaching the dielectric and ions already present on the surface. Such feedback is essential for controlling dQc down to 0.1% that is required to achieve similar accuracy in EOT monitoring. The basic ideas involved in time resolved corona CV metrology are discussed using the "Flask analogy" depicted in Fig. 1. In this analogy, the dielectric is represented by flask A. The goal is to determine the flask cross section, S (analogous to EOT), by measuring a change of the water level, Ah, caused by filling the flask with a known amount of water. The water dose is analogous to the corona dose, AQC, while the change of water level, dh, is analogous to the voltage change, dV. Flask B represents the semiconductor substrate of a dielectric film and is connected with flask A. Its cross section decreases with height, and for large heights it becomes much smaller than that of flask A. This is analogous to the "deep accumulation" condition. Flask B also connects at different heights to additional flasks representing the interface traps. At the initial stages, water that is poured to flask A fills predominantly the large flask B and the interface traps. With increasing water level, the interface traps become filled. In addition, the cross section of flask B decreases. This range, corresponding to deep accumulation, provides a favorable condition for measuring the cross section of flask A. However, in this water level range, h > hieak, a leakage appears that is analogous to the direct tunneling across the dielectric. MONITORING OF WATER LEVEL (VOLTAGE) FILLING At; MEASURING DELAY . MEASURING INTERVALS DOSE 1 t3 TIME FIGURE 1. "Flask analogy" of time resolved Corona C-V metrology of dielectric capacitance Cd and EOT. 161 The most important feature in Fig. 2 is the elimination of the leakage induced distortions in capacitance by the time-resolved technique. It is also seen that in the range of appreciable leakage the capacitance and oxide thickness could not be measured correctly by the standard corona method. The standard method [2] relies on differentiation of the voltage vs. corona charge curve, V-Q. This approach fails in the deep accumulation and deep inversion ranges and, therefore, cannot be used for extracting a dielectric capacitance. As pointed out in our recent discussion of leakage caused limitations [4], the standard corona measurement approach is limited to SiO2 with thicknesses above 2.5nm. The corona C-V measuring cycle includes a measurement of surface photovoltage, that is of the illumination induced change of the voltage [1,8]. The zero value of surface photovoltage corresponds to the flat-band condition and is marked in Fig. 2 on the voltage scale as VFB. If the voltage prior to any corona charge application is V0, then a difference in total corona charge placed on a dielectric surface between V0 and VFB is the total charge, denoted as dQTOT [8]. This is an important parameter sensitive to electric charges located in the dielectric (including the top dielectric surface) and also at the dielectric/semiconductor interface. It is of interest to note that the total charge is not obtainable in MOS C-V measurements. Further measurements are possible using a timeresolved procedure shown in the right side of the figure. A quick dosing of water is followed by monitoring of the water level transient. By extrapolation of measured transients back in time, one can determine the water level changes, Ah! and Ah2, corrected for leakage which occurs during a small delay between filling and measuring, At, that is a result of the finite speed of the filling-measuring apparatus. A limiting value of Ah that is obtained for large heights contains a negligible contribution from flask B. In corona C-V measurements performed in the high-field range of deep accumulation, this is analogous to a reduced contribution of space charge and interface traps, CSc + Qt, to the total capacitance, C. RESULTS AND DISCUSSION C-V Characteristics The corona C-V corresponding to a full range of semiconductor space charge, from deep accumulation to deep inversion, is shown in the upper portion of Fig. 2 for SiO2 on p-type silicon substrate with a dopant concentration NA = lei5 cm"3. The lower portion of Fig. 2 shows the corresponding leakage current density obtained during the same measurement cycle. The horizontal scale, for simplicity labeled "voltage", represents the contact potential difference, VCPD, measured with a vibrating probe as described in [1]. z.u .0 LL i o A / 1.0 _ s' \ t-Z.U -1.0 1 9 * VFB .•—.'* v0 . --.f . r, on -1.5 / '••••" I • • ••time resolved " ——— standard -2.0 " INTERFACE TRAPS ~ • • • • ••^ •0 s^"" **i <D 0 (0 Q. DEEP DEEP ACCUMULATION ^ 0.5 1.0 1 1 1 0 0.5 1.0 -0.5 1.5 ^ fQ1 woo "w 0) 2 CO fl) _j -20 -2.0 1 -1.5 1 -1.0 1 -0.5 * 1.5 Voltage [V] FIGURE 2. Corona C-V and Leakage current measured on 2.2nm thick SiO2 on p-type silicon. 162 Extraction of Dielectric Capacitance CD I I 1 1 —— 1—.»- • The static character of corona C-V and the demonstrated sensitivity of C-V to interface traps requires a modification of the extraction procedure for dielectric capacitance in comparison to that used in MOS C-V. In contrast to the entire MOS C-V curve analysis [7], the extraction of Cd from corona C-V uses only a high-field deep accumulation range of the characteristic. In the corresponding high negative corona limit, the dielectric field is about l.lMV/cm and the (CSc + Qt) contribution approaches 100 fiF/cm2. This value is much larger than Cd of 3.5uF/cm2 corresponding to Inm SiO2, thereby creating a favorable condition for extraction of Cd from the total capacitance equation: j— .............. T^ | 3.0- AAAAA LL "AA/AAaAAAA^AA A A A 8 2.01 Drt~4e13A/ A A Csc O §. 1.0(0 o nn -1.2 0 I p—j |-—^ I__| |__I ..._,_|— .... — ...4 -1 - -0.8 A . 1 1 -0.6 -0.4 1 -0.2 . A A 1 . 0 0.2 Voltage [V] FIGURE 3. The effect of flattening of corona C-V observed for large interface trap density. Empty and filled symbols correspond to nitrided oxides with similar EOT of about 1.1 nm but with Dit - 4el3 q/cm2V and Iel2 q/cm2V, respectively. c cd c< Effect of Interface Traps Interface traps, both of discrete energy level and with a continuous energy distribution, are determined in the corona C-V measuring cycle the same way as in the COCOS technique, described in detail in [8]. One shall notice, however, that the effect of traps on corona C-V is different from that in MOS C-V. The first difference stems from a true static nature of corona CV. Thus, the corona capacitance contains a contribution from all traps with a time response less than the corona charging/measuring cycle - about 1 s. In MOS measurement the capacitance is sensitive to traps with a time constant limited by the capacitance measuring frequency. For this reason, high frequency MOS measurements are used for the purpose of eliminating the contribution of traps to the measured capacitance. The second very important difference is due to a wafer treatment involved in the gate preparation necessary for MOS C-V measurement. The treatment (especially forming gas annealing) reduces interface trap density. In contrast to corona C-V wafers that are often measured just after oxidation without any additional processing. The static character and sensitivity of corona C-V to interface traps is illustrated in Fig. 3 with data obtained for nitrided oxides with similar EOT of about 1.1 nm but with very different interface trap density, Dit of 4el3 q/cm2V and Iel2 q/cm2V, respectively. It is seen that large Dit significantly flattens the corona C-V curve. This is consistent with a static capacitance equivalent circuit shown in the Fig. 3, where the oxide capacitance, Cox, is in series with CSc + Qt. 163 (2, Furthermore, CSc + Qt becomes a characteristic power function of the net surface charge and is independent of the dielectric thickness and the semiconductor substrate doping. This behavior of capacitance is similar to the high field MOS capacitance recently reported by R. Clerc et.al [6] in their study on characterization and modeling of MOS with an ultra-thin oxide. From this reference, we adopted the oxide capacitance extraction procedure and we found it working exceptionally well for a large range of dielectrics. We tested the procedure using a series of wafers with SiO2 on p-type Si. The nominal SiO2 thicknesses, given by the wafer supplier, were based on "initial optical thickness" measured immediately after oxidation in order to avoid effects of contamination and adsorption that increase the optical thickness. The example of the fitting curve together with the corona C-V data and corresponding leakage is shown in Fig. 4. The initial optical thickness of this dielectric was 1.25nm (average of 5-site measurement). This value compares very well with the EOT = 1.279nm extracted from corona C-V measured in the center of the wafer. Figure 5 compares the average values of 5-site corona C-V EOT with the corresponding initial optical thicknesses. It is evident that the adopted EOT extraction procedure gives excellent one to one agreement with the nominal SiO2 thickness. Effect of Moisture and MAC Figure 6 shows results for SiO2 on p-type Si measured for the first time within 1 day after oxidation and then remeasured two weeks later. It is seen that contamination of the dielectric with moisture and MAC during wafer storage shifts the voltage by more than 0.2 V in the positive direction. This shift is consistent with the dipole nature of adsorbed molecules [8]. It is also seen from Fig. 6 that this surface contamination has no effect on the oxide capacitance plateau in deep accumulation and the extracted EOT values. Note that both sets of data in Fig. 6 are fitted with the same curve, but simply shifted in voltage. It is also important to note that the initial optical elipsometric measurements for this wafer agreed well with the EOT. However, after two weeks of wafer storage the optical thickness increased by 0.39nm, more than 30%, while the corona EOT measurement was unchanged. It is thus evident that corona C-V can bring a solution to high-k monitoring problems discussed in ref. 3. CD = 2.697 fj.Bcm2; EOT = 1.279 nm 2.5 •"X •¥ £ * ^ \\ I1"5 S 1 • standard —— fitting n *; —————i—————i—————i—————i—————i————— -1.6 -1.4 -1.2 -0.8 -0.6 -0.8 4 V-^ o 61 o 01 c \ , Leakage [nA/cm2] -1.8 .8 -1.6 -1.4 -1.2 -1 Voltage [V] FIGURE 4. Experimental data illustrating new timeresolved corona C-V and standard corona C-V in deep accumulation with the corresponding leakage current shown in the bottom portion. Solid line is the fitting curve used to extract dielectric capacitance and EOT. z I CD = 1 .68 nF/cm2;EOT = 2.054 nm c$- s S. 3 e c s * , \ O ' * after storage 0 initial \ ^ \ \ —— fitting 1 \ * icitance[(aFj 0 \ 0.5 ————————|———————|———————|———————|——————— -1.3 -1.1 -0.9 -0.7 -0 -1 .5 2 Voltage [V] Initial Optical Thickness [nm] FIGURE 6. The effect of surface contamination during wafer storage on corona C-V. Note the same dielectric capacitance and EOT values are extracted from fitting both C-V curves. FIGURE 5. Correlation between EOT extracted with the present corona C-V procedure and the optical ellipsometric data measured just after oxidation. SiO2 films on p-type Si substrates. 164 research projects at Universities and non-industrial laboratories. o.u Ta205 EOT=0.69nm *r 5.0 Hf02 EOT=0.78nm oooo E 4.0 MA EOT=1.05nm « ®• 1 i m £ 3 o o '* ^® 3.0 • • 0 • *•* * » SrTiO3 2.0 ACKNOWLEDGEMENT %. *•_ °o \ o * ° ° • o *.o EOT=2.10nm o,* . *Sg$* * •• 1.0 The authors would like to thank Dr. George Brown from Sematech for enlightening discussions on monitoring of advanced gate dielectrics. . m REFERENCES •* *••••• X^...' 1. nn -3 -2 -1 0 +1 2. 3. Voltage [V] 4. FIGURE 7. Corona C-V characteristics measured for high-k dielectrics on p-type substrates. 5. High-K Dielectrics The corona C-V technique and EOT extraction method were applied to high-k dielectric films on ptype Si substrates. The results are shown hi Fig. 7. EOT in the sub-nanometer range were measured for Ta2O3 and HfO2; resulting in 0.69nm and 0.78nm, respectively. Nominal physical thicknesses given by suppliers were 4.0nm for Ta2O3, 4.6nm for HfO2, 3.0nm for AL2O3 and lOnm for SrTiO3. The comparison with corona EOT values gives the corresponding values of dielectric constant of 22.6, 23.0, 11.1 and 18.6, respectively. These values are in good agreement with literature data. 6. 7. 8. CONCLUSIONS The corona C-V method based on rapid corona charging and time-resolved non-contact measurement of dielectric potential with a vibrating contact potential probe provides a reliable means for electrical characterization of ultra-thin dielectrics. The method enables measurement of differential capacitance in the high-field range despite leakage neutralization of the corona charge. This high field range is found suitable for accurate extraction of dielectric capacitance and the corresponding EOT. The methodology was tested using SiO2 and subsequently applied to high-k dielectrics with EOT extending to the subnanometer regime. It is believed that the corona C-V EOT measurement should prove extremely valuable as electrical film characterization support for R&D of new dielectrics. We also trust that this very accurate and inexpensive metrology can be of interest for 165 Lagowski, J., Edelman, P., Inst. Phys. Conf. Ser. 160, 133-140 (1997). Schroder, D. K.. Mat. Sci. and Eng. B91-92, 196 (2002). Brown, A. E., Semiconductor International 25, 55 (2002). Edelman, P., et al., Mat. Sci. and Eng. B91-92, 211 (2002). Wilson, M., et al., "Study of Stress Induced Leakage Current in Thni Oxides Stressed by Corona Charging in Air: relationship to GOI Defects", in Structure and Electronic Properties of Ultrathin Dielectric Films on Silicon and Related Structures, edited by D.E. Buchanan et al., MRS Symosium Proceedings 592, Warrendale, PA, 2000, pp. 345-350. Cleve, R., et al., Solid-State Electronics 46, 407 (2002). Ahmed, K., et al., IEEE Trans. El. Devices 47, 1349 (2000). Wilson, M., et al. "COCOS (Corona Oxide Characterization of Semiconductor) Metrlogy: Physical Principles and Applications", in Gate Dielectric Integrity: Material, Process, and Tool Qualification, ASTM STP1382, edited by D.C. Gupta and G.A. Brown, American Society for Testing and Materials, West Conshohocken, PA, 1999, pp. 74-90.
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