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In this section, the physical and electrical characteristics of MOS capacitors using MOCVD HfAlO dielectric were discussed.

2-3-1 C-V Characteristic

Fig. 2-4~2-11 show the relationship between the sweep voltage and capacitance for Hf1-xAlxO MOS Capacitors. We have several conditions for Hf1-xAlxO MOS capacitors. Then we measure C-V curves, and use a systematic methodology to extract the accurate flat band voltage of Hf1-xAlxO MOS capacitors for interfacial state density (Fig. 2-21).We found that the higher PDA temperature, the thicker dielectric, the higher interface density, therefore the capacitance decreases. We also found that the H1A2 C-V curves are better than others.

2-3-2 I-V Characteristic

We also measure I-V curves, such as Fig. 2-12~2-19 illustrate. We found that the more Hf component the more leakage current, and higher PDA temperature the higher gate leakage current. This is because that more Hf component more grain boundaries.

Fig. 2-20 shows that the gate leakage current comparison between H1A2 and Al2O3

sample with the same condition (As-dep., 600oC PDA and 800oC PDA). We found

15

that they are almost the same.

2-3-3 CET Characteristic

From the C-V illustrations (Fig. 2-4~2-11), we not only can calculate the Vfb for each sample, but also the CET for each sample. So we plot the Fig. 2-22 which shows the relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and each sample for all conditions. We discovered that the more Hf component the higher gate leakage current Jg@Vfb-2V(A/cm2), this is because that the more Hf component the more grain boundaries. The Fig. 2-23 shows the relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and the CET for each samples with all PDA conditions.

We found that the Al-rich-Hf1-xAlxO capacitors are better than Hf-rich-Hf1-xAlxO ones in the relationship between gate leakage current and CET.

From the two pictures (Fig. 2-22 and 2-23), we extract the Al-rich-Hf1-xAlxO capacitors are better, so we discuss the Al-rich-Hf1-xAlxO characteristics especially.

Fig.2-24 shows the relationship between CET (nm) and each Al-rich samples with all PDA conditions, Fig. 2-25 shows the relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and each Al-rich-Hf1-xAlxO samples with all PDA conditions, and Fig. 2-26 shows the relationship between the gate leakage current Jg@Vfb-1.5V(A/cm2) and each Al-rich-Hf1-xAlxO samples with all PDA conditions. From Fig. 2-24 and Fig.

2-25, we can combine them to the Fig. 2-27 which shows that the relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and the CET for each samples with all PDA conditions. We can obviously find the two samples H1A2 (As-dep.) and H1A2 (700oC PDA) with the lowest CET and the lowest gate leakage current Jg@Vfb-2V(A/cm2) from Fig. 2-27, so we decided the four conditions (H1A2 As-dep., H1A2 700oC PDA, Al2O3 As-dep., and Al2O3 700oC PDA) are our the best blocking layer for SONOS-type memory in next chapter. We cast the characteristics of

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Al-rich-Hf1-xAlxO dielectrics capacitors in Table 2-3.

2-4 Summary

In this chapter, we observed that Al-rich Hf1-xAlxO dielectric capacitors have lower interfacial state density, lower gate leakage current Jg@Vfb-2V(A/cm2) and Jg@Vfb-1.5V(A/cm2), and lower CET than Hf-rich ones at the same condition.

Therefore we optimized the condition for the SONOS-type memory blocking layer.

According to our data, we choose A (Al2O3: As-dep. and 700oC PDA) and H1A2 (HfAlO: As-dep. and 700oC PDA) for our blocking layer of SONOS-type memory.

Dielectric

Table 2-1 Selected material and electrical properties of high-k gate dielectrics.

Data compiled from Robertson [2.5], Gusev et al. [2.4], Hubbard and Schlom [2.3], and other sources.

Fig. 2-1 Bandgap and band alignment of high k gate dielectrics with respect to silicon. Data from Robertnson [2.5], with permission. The dashed line represents 1eV above/below the conduction/valence bends.

Fig. 2-2 The process flow of the Hf1-xAlxO MOS capacitors. On the right: the different flow rates and the dielectric Hf/Al component ratio analyzed by XPS method.

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Sample

Split Condition H H10A1 H8A1 H6A1 H2A1 H1A1 H1A2 A

As-dep.

600oC PDA ● ● ● ● ● ● ● ●

700oC PDA ▲ ▲ ▲ ▲

800oC PDA ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆

900oC PDA ★ ★ ★ ★

Table 2-2 Split table for MIS Capacitors using MOCVD Hf1-xAlxO Dielectric.

0 2 4 6 8 10

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0

Hf/Al ratio in Hf 1-xAl xO

Hf/Al precursor rate

Fig. 2-3 The relationship between Hf/Al precursor rate and Hf/Al ratio in Hf1-xAlxO.

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-3 -2 -1 0 1 2 3

Fig. 2-4 The C-V curves of Al2O3 dielectric MOS capacitor.

-3 -2 -1 0 1 2 3

Fig. 2-5 The C-V curves of H1A2 (Hf/Al = 0.11) dielectric MOS capacitor.

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-3 -2 -1 0 1 2 3

Fig. 2-6 The C-V curves of H1A1 (Hf/Al = 0.23) dielectric MOS capacitor.

-3 -2 -1 0 1 2 3

Fig. 2-7 The C-V curves of H2A1 (Hf/Al = 0.55) dielectric MOS capacitor.

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-3 -2 -1 0 1 2 3

Fig. 2-8 The C-V curves of H6A1 (Hf/Al = 3) dielectric MOS capacitor.

-3 -2 -1 0 1 2 3

Fig. 2-9 The C-V curves of H8A1 (Hf/Al = 4) dielectric MOS capacitor.

21

-3 -2 -1 0 1 2 3

Fig. 2-10 The C-V curves of H10A1 (Hf/Al = 5.67) dielectric MOS capacitor.

-3 -2 -1 0 1 2 3

Fig. 2-11 The C-V curves of HfO2 dielectric MOS capacitor.

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-4 -3 -2 -1 0 Gate leakage current J g

(

A/cm2

)

Fig. 2-12 The I-V curves of Al2O3 dielectric MOS capacitor.

-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 Gate leakage current J g

(

A/cm2

)

Fig. 2-13 The I-V curves of H1A2 (Hf/Al = 0.11) dielectric MOS capacitor.

23

-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

Fig. 2-14 The I-V curves of H1A1 (Hf/Al = 0.23) dielectric MOS capacitor.

-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

Gate leakage current J g

(

A/cm2

)

Voltage(V)

Fig. 2-15 The I-V curves of H2A1 (Hf/Al = 0.55) dielectric MOS capacitor.

24

-4 -3 -2 -1 0

Fig. 2-16 The I-V curves of H6A1 (Hf/Al = 3) dielectric MOS capacitor.

-4 -3 -2 -1 0 Gate leakage current J g

(

A/cm2

)

Fig. 2-17 The I-V curves of H8A1 (Hf/Al = 4) dielectric MOS capacitor.

25

-4 -3 -2 -1 0 Gate leakage current J g

(

A/cm2

)

H10A1 As-dep.

600oC PDA 800oC PDA

Fig. 2-18 The I-V curves of H10A1 (Hf/Al = 5.67) dielectric MOS capacitor.

-4 -3 -2 -1 0 Gate leakage current J g

(

A/cm2

)

Fig. 2-19 The I-V curves of HfO2 dielectric MOS capacitor.

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-3 -2 -1 0

Fig. 2-20 The gate leakage current comparison between H1A2 and Al2O3 with the same condition (As-dep., 600oC PDA and 800oC PDA).

1011 1012 1013

Al-rich-Hf1-xAlxO (x=0.8-1) Hf-rich-Hf1-xAlxO (x=0-0.25)

Interfacial state density D it(cm-2 eV-1 )

Al

Fig. 2-21 The relationship between interfacial state density Dit and PDA conditions.

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10-10

Hf-rich-HfxAl1-xO (x=0.75-0.85) Al-rich-Hf

xAl

1-xO (x=0.1-0.2)

PDA conditions

Gate leakage current J g@V FB-2 V(A/cm2 )

900oC

Fig. 2-22 The relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and each sample for all conditions.

20 30 40 50 60 70 80

Hf-rich-Hf1-xAlxO (x=0-0.25)

Al-rich-Hf1-xAlxO (x=0.8-1)

CET (nm)

Gate leakage current J g@V FB-2 V(A/cm2 )

Fig. 2-23 The relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and the CET for each samples with all PDA conditions.

28

1

Fig. 2-24 The relationship between CET (nm) and each Al-rich-Hf1-xAlxO samples with all PDA conditions.

10-10

Hf/Al = 3.5/6.5 (H2A1)

Hf/Al = 1.9/8.1 (H1A1)

Hf/Al = 1.0/9.0 (H1A2)

PDA conditions

Gate leakage current J g@V FB-2 V(A/cm2 )

Fig. 2-25 The relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and each Al-rich-Hf1-xAlxO samples with all PDA conditions.

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10-9 10-8 10-7 10-6

Hf/Al = 3.5/6.5 (H2A1)

Hf/Al = 1.9/8.1 (H1A1)

Hf/Al = 1.0/9.0 (H1A2) 900oC PDA conditions

Gate leakage current J g@V FB-1.5 V(A/cm2 )

800oC 700oC

600oC As-dep.

Fig. 2-26 The relationship between the gate leakage current Jg@Vfb-1.5V(A/cm2) and each Al-rich-Hf1-xAlxO samples with all PDA conditions.

2 3 4 5 6 7

Gate leakage current J g@V FB-2 V(A/cm2 )

Hf/Al = 1.0/9.0 (H1A2) Hf/Al = 1.9/8.1 (H1A1)

CET (nm)

Hf/Al = 3.5/6.5 (H2A1)

Fig. 2-27 The relationship between the gate leakage current Jg@Vfb-2V(A/cm2) and the CET for each samples with all PDA conditions.

30

31

Al2O3(As-dep.) 44.8 0.89 1.3x1011 1.9x10-9 6.3x10-10

H1A2(As-dep.) 28.2 0.6 4x10

11

H1A1(As-dep.) 35.3 0.3 4.2x1012 3.7x10

-9

1.7x10

-9

H1A1(700oC PDA) 37.3 0.62 4.7x1012 10-7 8.1x10-9

H2A1(As-dep.) 35.9 0.44 10

12 Table 2-3 The characteristics of Al-rich-Hf1-xAlxO dielectrics capacitors.

Chapter 3

Characteristics of SONOS-type Memory with

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