Short summary - Electrical characteristics for HfO 2 with nitridation plasma treatment

Chapter 4 Results and Discussion

4.2 Electrical characteristics for HfO 2 with nitridation plasma treatment

4.2.3 Short summary

Fig. 4-19 and Fig. 4-20 shows the comparison of C-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-21 and Fig. 4-22 showed the leakage current density comparison of samples with and without PDA treatment.

Fig. 4-23 and Fig. 4-24 showed the C-V and the J-V characteristics of samples with various process treatments such as PDA treatment, fluorination treatment, and nitridation treatment. We compared with these treatment and without on electrical characteristics.

In this chapter, we demonstrate that samples treated by PDA treatment and nitridation treatment were the best choice.

4.3 Electrical characteristics for HfO

with CF

plasma treatment and N

plasma treatment

There are four kinds of plasma treatment with different source gas (i.e. CF4, N2, NH3, and N2O) and they were treated for different process time (i.e. 10 sec, 20sec, 30sec, 40sec, and 120sec).

4.3.1 Electrical characteristics for HfO

with CF

plasma treatment and N

plasma treatment but without PDA treatment

Fig. 4-25 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2 plasma for 30 sec and 90 sec. The capacitor treated in CF4 for 10 sec and N2 for 90 sec shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and N2 plasma all present the larger values than the capacitors without whole plasma process. This phenomenon indicates that dual plasma treatment was workable to improve the capacitance. The factor of improvement might be from that the fluorine and nitrogen can repair defect and dangling bonds.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 second and N2 plasma for 30 sec and 90 sec from 0V to -2V are described in Fig. 4-26. The gate leakage current density treated N2 plasma 90 sec shows the minimum current density among these conditions. The lower leakage shows that the weak structure of interface must be fixed by the plasma nitridaiton.

The hysteresis of C-V characteristics are shown in Fig. 4-27, and Fig.4-28 for the samples with fluorination and with 30 and 90 sec N2 plasma treatment , respectively.

The hysteresis characteristic could be improved by various plasma nitridation process.

4.3.2 Electrical characteristics for HfO

with CF

plasma treatment, N

plasma treatment and PDA treatment

Fig. 4-29 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2 plasma for 30 sec and 90 sec with PDA treatment. The capacitor treated in CF4 for 10 sec and N2 for 90 sec with PDA treatment shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and N2 plasma all present the larger values than the capacitors without whole plasma process.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2

plasma for 30 sec and 90 sec with PDA treatment from 0V to -2V are described in Fig.

4-30. The gate leakage current density treated in CF4 plasma 10 sec and N2 plasma 90 sec with PDA treatment shows the minimum current density among these conditions.

The hysteresis of C-V characteristics are shown in Fig. 4-31 and Fig. 4-32 for the samples with fluorination, PDA treatment, and with 30 and 90 sec N2 plasma treatment, respectively. The hysteresis characteristic could be improved by various plasma nitridation process.

4.3.3 Short summary

Fig. 4-33 and Fig. 4-34 shows the comparison of C-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-35 and Fig. 4-36 shows the comparison of C-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-37 and Fig. 4-38 showed the C-V and the J-V characteristics of samples with various process treatments such as PDA treatment, fluorination treatment, and

nitridation treatment. We compared with these treatment and without on electrical characteristics.

In this chapter, we demonstrate that samples treated by PDA treatment, fluorination, and nitridation treatment were the best choice.

4.4 Electrical characteristics for HfO

with CF

plasma treatment and N

O plasma treatment

There are four kinds of plasma treatment with different source gas (i.e. CF4, N2, NH3, and N2O) and they were treated for different process time (i.e. 10 sec, 20sec, 30sec, 40sec, and 120sec).

4.4.1 Electrical characteristics for HfO

with CF

plasma treatment and N

O plasma treatment but without PDA treatment

Fig. 4-39 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2O plasma for 30 sec and 90 sec. The capacitor treated in CF4 for 10 sec and N2O for 90 sec shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and N2O plasma all present the larger values than the capacitors without whole plasma process. This phenomenon indicates that dual plasma treatment was workable to improve the capacitance. The factor of improvement might be from that the fluorine and nitrogen can repair defect and dangling bonds.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 second and N2O plasma for 30 sec and 90 sec from 0V to -2V are described in Fig. 4-40. The gate leakage current density treated N2O plasma 90 sec shows the minimum current density among these conditions. The lower leakage shows that the weak structure of interface must be fixed by the plasma nitridaiton.

The hysteresis of C-V characteristics are shown in Fig. 4-41 and Fig.4-42 for the samples with fluorination and with 30 and 90 sec N2O plasma treatment , respectively.

The hysteresis characteristic could be improved by various plasma nitridation process.

4.4.2 Electrical characteristics for HfO

with CF

plasma treatment, N

O plasma treatment and PDA treatment

Fig. 4-43 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2O plasma for 30 sec and 90 sec with PDA treatment. The capacitor treated in CF4 for 10 sec and N2O for 90 sec with PDA treatment shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and N2O plasma all present the larger values than the capacitors without whole plasma process.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 sec and N2O plasma for 30 sec and 90 sec with PDA treatment from 0V to -2V are described in Fig. 4-44. The gate leakage current density treated in CF4 plasma 10 sec and N2O plasma 90 sec with PDA treatment shows the minimum current density among these conditions.

The hysteresis of C-V characteristics are shown in Fig. 4-45, and Fig.4-46 for the samples with fluorination, PDA treatment, and with 30 and 90 sec N2O plasma treatment , respectively. The hysteresis characteristic could be improved by various plasma nitridation process.

4.4.3 Short summary

Fig. 4-47 and Fig. 4-48 shows the comparison of C-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-49 and Fig. 4-50 shows the comparison of J-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-51 and Fig. 4-52 showed the C-V and the J-V characteristics of samples with various process treatments such as PDA treatment, fluorination treatment, and nitridation treatment. We compared with these treatments and without on electrical

characteristics.

In this chapter, we demonstrate that samples treated by PDA treatment, fluorination, and nitridation treatment were the best choice.

4.5 Electrical characteristics for HfO

with CF

plasma treatment and NH

plasma treatment

There are four kinds of plasma treatment with different source gas (i.e. CF4, N2, NH3, and N2O) and they were treated for different process time (i.e. 10 sec, 20sec, 30sec, 40sec, and 120sec).

4.5.1 Electrical characteristics for HfO

with CF

plasma treatment and NH

plasma treatment but without PDA treatment

Fig. 4-53 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and NH3 plasma for 30 sec and 90 sec. The capacitor treated in CF4 for 10 sec and NH3 for 90 sec shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and NH3 plasma all present the larger values than the capacitors without whole plasma process. This phenomenon indicates that dual plasma treatment was workable to improve the capacitance. The factor of improvement might be from that the fluorine and nitrogen can repair defect and dangling bonds.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 second and NH3 plasma for 30 sec and 90 sec from 0V to -2V are described in Fig. 4-54. The gate leakage current density treated NH3 plasma 90 sec shows the minimum current density among these conditions. The lower leakage shows that the weak structure of interface must be fixed by the plasma nitridaiton.

The hysteresis of C-V characteristics are shown in Fig. 4-55, and Fig.4-56 for the samples with fluorination and with 30 and 90 sec NH3 plasma treatment , respectively.

The hysteresis characteristic could be improved by various plasma nitridation process.

4.5.2 Electrical characteristics for HfO

with CF

plasma treatment, NH

plasma treatment and PDA treatment

Fig. 4-57 reveals the capacitance-voltage (C-V) characteristics of MIS capacitor treated in CF4 plasma for 10 sec and NH3 plasma for 30 sec and 90 sec with PDA treatment. The capacitor treated in CF4 for 10 sec and NH3 for 90 sec with PDA treatment shows the maximum capacitance density among these samples with different process times. In addition, other samples which treated in CF4 plasma and NH3 plasma all present the larger values than the capacitors without whole plasma process.

The J-V characteristics of MIS capacitor treated in CF4 plasma for 10 sec and NH3 plasma for 30 sec and 90 sec with PDA treatment from 0V to -2V are described in Fig. 4-58. The gate leakage current density treated in CF4 plasma 10 sec and NH3

plasma 90 sec with PDA treatment shows the minimum current density among these conditions.

The hysteresis of C-V characteristics are shown in Fig. 4-59, and Fig. 4-60 for the samples with fluorination, PDA treatment, and with 30 and 90 sec NH3 plasma treatment, respectively. The hysteresis characteristic could be improved by various plasma nitridation process.

4.5.3 Short summary

Fig. 4-61 and Fig. 4-62 shows the comparison of C-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-63 and Fig. 4-64 shows the comparison of J-V curves of the samples with and without PDA treatment on ZrO2 film in O2 ambient at 500°C for 5 minute.

Fig. 4-65 and Fig. 4-66 showed the C-V and the J-V characteristics of samples with various process treatments such as PDA treatment, fluorination treatment, and nitridation treatment. We compared with these treatment and without on electrical characteristics.

In this chapter, we demonstrate that samples treated by PDA treatment, fluorination, and nitridation treatment were the best choice.

Fig. 4-67 shows the capacitance-voltage (C-V) characteristics of MIS capacitors combined CF4 plasma treatment with N2, NH3, or N2O plasma treatment at optimal condition.It is indicated that the capacitance treated in CF4 plasma for 10 sec and N2

plasma for 90 sec shows the most excellent value among these samples. The films with the N2 plasma treatments showed higher capacitances than those with the N2O plasma treatments, because the N2O treatment caused increased growth of the interfacial silicate layer. The samples treated in NH3 plasma exhibited the highest interface trap density compared with the samples treated by the other treatments. It was due to the hydrogen related traps (-H, -OH, and N-H) formed on the surface of Si substrate. This suggests that remote-plasma N2 treatment is the optimal process to obtain an increased dielectric constant.

The J-V characteristics of MIS capacitors combined CF4 plasma treatment with N2, NH3, or N2O plasma treatment at optimal condition in Fig. 4-68. The gate leakage current density treated in CF4 plasma 10 sec and N2O plasma 90 sec shows the minimum current density among these conditions. The samples with nitridation and PDA treatments demonstrated lower leakage current due to the Si-O and Si-N bonds formation. The bonding strength comparisons as below: Si-O bond is 8.42 eV. Si-N bond is 4.75 eV. Si-Si bond is 3.38 eV. Si-H bond is 3.18 eV. We understood that bonding strength of Si-N and Si-O bonds are so stronger that the leakage current was lower. The leakage current of samples without plasma treatment is large due to the poor interfacial layer characteristic.

Chapter 5 Conclusions and future work

5.1 Conclusions

In this thesis, various surface treatments such as PDA (post deposition annealing), fluorination, and nitridation are present. It is evidence that the ZrO2(interfacial layer) treated by PDA treatment at 500 °C for 5 min can effectively reduce leakage current, hysteresis, and can improve capacitance value. After PDA treatments, the high K dielectric quality was improved, and the reliability therefore superior.

The next chapters, characteristics of MIS capacitors that combine CF4 plasma treatment with N2, NH3, or N2O plasma treatment have been investigated. Most of the plasma treatment samples can promote the electrical characteristics and reliability until the plasma damage or the growth of interfacial layer happened. Among these treatments, the samples treated in CF4 plasma for 10 sec and N2, NH3, or N2O plasma for 90 sec represent significantly great improvement, such as good capacitance, reduced leakage current and smaller C-V hysteresis. In addition, the N²O or NH3 plasma treatment has the lower leakage current than N2 plasma for HfO². The reason is that the samples using N²O plasma treatment will introduce oxygen bonding to form additional interfacial layer so that the capacitance will be lower. But, the thicker oxidation layer generates a good resistance against leakage current. The bonding strength comparisons as below: Si-O bond is 8.42 eV. Si-N bond is 4.75 eV. Si-Si bond is 3.38 eV. Si-H bond is 3.18 eV. We understood that bonding strength of Si-N and Si-O bonds are so stronger that the leakage current was lower. The samples treated in NH3 plasma exhibited the highest interface trap density compared with the samples treated by the other treatments. It was due to the hydrogen related traps (-H, -OH, and N-H) formed on the surface of Si substrate. Finally, in this thesis, the various surface treatments such as without treatment,

PDA treatment, fluorination, and nitridation are compared and studied. We demonstrate that samples treated by PDA treatment at 500 °C for 5 min, CF4 plasma pretreatment for 10 sec, and N2 plasma treatment for 90 sec were the best choice.

5.2 Future work

Although the effect of the PDA treatment, plasma nitridation, and fluorination to the electrical characteristics and reliabilities of ZrO2/HfO2 stack dielectric thin films has been examined in this research, there are still several issues that could investigated in the future:

1. The reason of leakage current mechanism:

We must try to research the mechanism for leakage current with SE, FP, F-N tunneling effect in Hf-based thin film further. Therefore, we can realize the mechanism of leakage and effectively prevent leakage problem.

2. Material Analysis:

We can use some material analysis methods such as TEM, SIMS, AFM to know the thin film composition precisely and verify the phenomenon observed from C-V and J-V curve, SILC, CVS etc.

3. Devices fabrication with the above results:

The optimum condition will be used to manufacture MOS device in the future.

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在文檔中不同表面處理對二氧化鉿與二氧化鋯推疊式高介電常數材料薄膜之效果 (頁 45-107)