Temperature Characteristics of the fluorine passivation

Chapter 3 Characteristics of HfO 2 Inter-Poly Dielectrics with Fluorine

3.3.5 Temperature Characteristics of the fluorine passivation

In this part, the carrier transportation of poly gate with and without fluorine incorporation characteristics will by investigating. Figure 3.15 (a), (b), (c), (d) were shown temperature dependence of gate current density at 1.73 MV/cm of HfO2

inter-poly capacitors with surface fluorine passivation that under floating gate and control gate both polarities. The FG and CG leakage current increase with increasing measuring temperature under both poly-gate incorporation of fluorine, show obvious high temperature dependence. As the fluorine implant dosage increases to 5e13cm^-2 and 1e15cm^-2 during FG and CG, respectively. The increase in the effectively trapping level is easily observed, meaning that most of the shallow traps in HfO2 IPD film with fluorine passivation can effectively resist leakage current density in higher temperature. Besides, the low leakage current density can ascribe the bulk defect really perfect with fluorine repair. Comparing the with fluorine and without fluorine passivation samples, we find, the poly gate leakage current density of the SSFI HfO2

IPD films is about one to two orders less than that of samples without any fluorine implantation in over 125℃. The schottky emission current of poly gate depended on temperature variation. However, because the barrier height extracted from Schottky

is more about two orders thermal stability compared to HfO2 films. Table 1.1 show both of HfO2 and Al2O3 IPDs have good thermodynamic stability with poly-Si in high temperature. The high heat of formation, Al2O3 films has the highest heat of formation (399 Kcal/mole) than HfO2 films (271 Kcal/mole), the mean are not be oxidized easily.

Besides, Al2O3 films for free energy chemical reduction function is (63.4 Kcal/mole) higher than that HfO2 films (47.6 Kcal/mole), causing Al2O3 IPDs more thermal stable about one order compare with HfO2 IPD. By the result, the thermal stability of HfO2

IPDs and Al2O3 IPDs both are much improved owing to the incorporation of fluorine.

3.4 Summary

In this thesis, we demonstrate that incorporation of SSFI method by N2 950℃

RTA activation after HfO2 IPDsdeposition remarkably improves inter-poly dielectrics behavior such as significantly less EOT, charge trapping rate and interface states generation. We found that fluorine tends to segregation into the poly/ HfO2 and poly interface and fluorine atoms diffusion into lattice generation strong Si-F, Hf-F and Al-F bonds compared to Si-H, Hf-H and Al-H. Both floating gate and control gate compare, we evidence that fluorine more effective passivation at poly/ HfO2 (FG), beside C-V, EOT and k value characteristics. Flash memories with Al2O3 IPDsand HfO2 IPDs can clearly exhibit significant improvement in data retention, leakage current and charge-to-breakdown (QBD) to replace conventional silicon oxide or oxide/nitride/oxide (ONO) IPDs. Table 3.1 lists several physical and electrical parameters, including EOT, κ-value, interfacial layer thickness, effective breakdown field and 63%-failure QBD values of the HfO2 IPD capacitors with surface fluorine passivation under positive and negative CVS at various fluorine dosage. After understanding flash memories trend need, the thesis is adopted as Al2O3 IPDs and

proved as promising candidates for the gate dielectrics of 45nm and 32nm generation stacked-gate flash memories device.

As the HfO2 IPD capacitors process had completed the work. We used high-resolution transmission electron microscopy (HRTEM) to confirm HfO2 IPD thickness and interfacial layer thickness. Before HRTEM, We must be cutting and digging a hole with focused ion beam (FIB). Figure.3.17 shows the FIB cross-sectional images of HfO2 IPD capacitors. The FIB top images of HfO2

inter-poly dielectric device thickness must be smaller than 500Å to do HRTEM. After finishing FBI, Figure. 3.18 show the TEM all cross-sectional images of HfO2

inter-poly dielectric. The HfO2 dielectric thickness is about 120 Å ~150Å. Figure.

3.19 show FG with 5E13cm^-2.Sample not only smoothes interface but also reduces interfacial layer thickness.

Table 3.1 EOT, κ-value, effective breakdown field and 63%-failure QBD values of the HfO2 capacitors with surface fluorine passivation under positive and negative CVS at various fluorine dosage effects.

EBD

(MV/cm)

63% QBD (C/cm²) F Dosage (cm^-2) κ EOT

(Å)

positive negative positive negative

0 12.6 46.6 7.73 7.21 0.00271 0.0035

P-type Si Substrate 2000Å Buffer Oxide

2000Å n⁺Poly-I 2000Å n⁺Poly-II

TEOS 5000Å Al Metal Pad

SiN_x~10Å 100Å Al₂O₃

Fig. 3.1 Cross-sectional view of HfO2 inter-poly capacitors with surface fluorine passivation. The fluorine was implanted on Poly-I (Floating Gate) and Poly-II (Control Gate).

N2 950ºC PDA 30sec

RCA cleaning and

2000Å buffer oxide 2000Å Poly-II deposition 2000Å Poly-I

deposition Poly-II Phosphorous 5E15 20KeV Poly-I Phosphorous

5E15 20KeV Fluorine 5E13 to 5E15 20KeV and activation Fluorine 1E12 to 1E14

10KeV and activation TEOS 5000Å deposition STD cleaning and

HF-last Gate and metal line

patterning 100Å HfO2 IPD

deposition

Fig. 3.2 Key process steps of HfO2 inter-poly capacitors with surface fluorine passivation.

- 2 . 0 - 1 . 5 - 1 . 0 - 0 . 5 0 . 0 0 . 5 1 . 0 1 . 5 2 . 0

Fig. 3.3 (a) C-V characteristics of HfO2 floating gate inter-poly capacitors with surface fluorine passivation effect is beneficial in scaling EOT that fluorine dosage

-- --

Equivalent Oxide Thickness ( nm )

H F O

Equivalent Oxide Thickness ( nm )

w /o F

-- --

Equivalent Oxide Thickness ( nm )

H F O

2 F lo a tin g G ate a n d C o n tro l G a te

(c)

Fig. 3.4 The average EOT of HfO2 IPD capacitors with surface fluorine passivation under(a) floating gate (b) control gate (c) floating gate and control gate compared.

- 2 . 0 - 1 . 5 - 1 . 0 - 0 . 5 0 . 0 0 . 5 1 . 0 1 . 5 2 . 0

G

D

s

S

Floating Gate High-k IPD

Control Gate

n

P-type Si sub Tunneling Oxide

n

+

C1 V1

- +

V2 C2

+

V

- -

V=V

₁

+V

₂

V

₂

=[C

₁

/(C

₁

+C

₂

)]V if C

₁

>>C

₂

then C

₁

/(C

₁

+C

₂

) ~1 Coupling ratio ↑

B

(a) (b) Fig. 3.6 (a) The stacked-gate flash memories structure. (b) A formula for the IPD capacitors coupling ratio.

- 1 0 - 8 - 6 - 4 - 2 0 2 4 6 8 1 0

Fig. 3.7 (a) J-V characteristics of HfO floating gate inter-poly capacitors with surface

3.30

Fig. 3.8 The dosage-average breakdown voltage images of HfO2 capacitors with surface fluorine passivation under (a) Positive VG floating gate (b) Negative VG

floating gate (c) Positive VG control gate (d) Negative VG control gate.

1 E - 1 0

Fig. 3.9 The dosage-average breakdown voltage images of HfO2 capacitors with surface fluorine passivation under (a) Positive VG (b) Negative VG floating gate and control gate comparison.

Current Density ( A/ cm2 )

(a)

(b)

Fig. 3.11 (a) The fluorine concentration and depth profiles for the three individual implants, and their sum for 1％ fluorine in 1500 SiO2 film [94]. (b) SIMS depth profile of 19 F- in the local F sample before and after FGA (4oo℃, 30 min). F tends to segregate at HfO2/ SiO2 interfaceafter FGA. F diffuses toward HfO2/ SiO2 interface [95].

1 1 0 1 0 0 1 0 0 0

Fig. 3.12 As-fabrication trap densities evaluation at 2 V constant voltage stress

1 1 0 1 0 0 1 0 0 0

Fig. 3.12 As-fabrication Positive trap densities evaluation at 2 V constant voltage stress (CVS) of HfO2 Control Gate inter-poly capacitors with surface fluorine passivation effect that fluorine dosage ranging from 5e13cm^-2to 1e15cm^-2 at 20keV under (c) positive 2V (d) negative 2V trap densities. HfO2 inter-poly capacitors with fluorine passivation can reduce As-fabrication trap densities.

1 E - 1 0 1 E - 9 1 E - 8 1 E - 7 1 E - 6 1 E - 5 1 E - 4 1 E - 3 0 . 0 1 0 . 1 1 1 0 1 0 0

Fig. 3.13 QBD Weibull plots of HfO2 inter-poly capacitors with surface fluorine passivation effect under (c) positive CVS and (d) negative CVS that fluorine dosage ranging from 5e13cm^-2to 1e15cm^-2 at 20keV. HfO2 inter-poly dielectric with surface fluorine passivation effect can significantly increase QBD in Control gate.

1 E - 1 0 1 E - 9 1 E - 8 1 E - 7 1 E - 6 1 E - 5 1 E - 4 1 E - 3 0 . 0 1 0 . 1 1 1 0 1 0 0

4 0 6 0 8 0 1 0 0 1 2 0

Fig. 3.15 Temperature dependence of gate current density at 1.73 MV/cm of HfO2

inter-poly capacitors with surface fluorine passivation that fluorine dosage ranging from 1e12cm^-2to 1e14cm^-2 at 10keV in Floating Gate under (a) positive and (b) negative polarities.

4 0 6 0 8 0 1 0 0 1 2 0 Current Density @1.73MV/CM( A/cm2 )

(℃)

(d)

4 0 6 0 8 0 1 0 0 1 2 0 Current Density @ 1.73MV/CM( A/cm2 )

H F O₂ F lo a t in g G a t e a n d C o n t r o l G a t e

Fig. 3.16 The Temperature images of HfO2 capacitors with surface fluorine passivation under (a) Positive VG (b) Negative VG floating gate and control gate compare.

Fig. 3.17 The FIB cross-sectional images of HfO2 inter-poly capacitors.

n⁺-poly FG

p-Sub interfacial layer

Wet oxide n⁺-poly CG

HfO2 IPD

FG 5E13

HfO2 IPD

Fig. 3.19 The TEM cross-sectional images of HfO2 inter-poly capacitors about 150Å with FG 5E13 cm^-2sample.

CHAPTER 4 Conclusions and Recommendations for Future Works

4.1 Conclusions

According to ITRS roadmap, the conventional SiO2 can’t meet the requirement due to the large tunneling current for thickness small than 20Å. So, a continuously scaling of the tunnel oxide and IPD thickness for Flash memories is needed to obtain high-k materials. In tradition, high-k materials are imperfect materials. In this thesis, it was found that the electrical properties of Al2O3 and HfO2 IPD strongly depend on the fluorine passivation. Form the experiment results, the fluorine passivation with FG (5E13) and CG (5E15) are the best condition which to make Al2O3 and HfO2 IPD film working moer effectively. As a result, the smoother interface and smaller electron trapping rate contribute to the drastically reduced leakage current, enhanced effective breakdown field, charge to breakdown (QBD) and significantly reduce the charge loss of leakage current from floating gate at 150℃ by using MOCVD.

Finally, the fluorine passivation effects of Al2O3 and HfO2 IPD were found to

4.2 Recommendations for Future Works

1. More HRTEM images to evidence thickness variation and interfacial layer reaction.

2. More physical analyses are found with the Fluorine passivation effect in other high-K materials in Future.

3. The Fluorine passivation effect Dosage of Al2O3 IPD and HFO2 IPD can use in Flash menories or other devices.

4. The fluorine passivation of stacked-gate flash memories with IPD to study the device characteristics, including program/erase speed, retention time and charge.

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