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Crystalline Oxide Semiconductor Using CAAC-IGZO and Its Application
Crystalline Oxide Semiconductor Using CAAC-IGZO and Its Application
Crystalline Oxide Semiconductor Using CAAC-IGZO and Its Application
S. Yamazaki
Introduction
It has been approximately 30 years since Kimizuka et al. synthesized In-Ga-Zn oxide
(IGZO) for the first time (1). As a device using IGZO as a semiconductor active layer, the
report of 1995 which evaluates the electric characteristics of an oxide semiconductor field
effect transistor (FET) and suggests using oxide semiconductor FET containing In, Ga,
and Zn (2) and the report of 2004 on amorphous IGZO thin film transistor (TFT) (3) are
known.
Nomura et al. reported an FET using a single crystal IGZO film with a ZnO buffer
layer (4), and reported the existence of an amorphous oxide semiconductor (a-OS) and its
FET characteristics (5). In addition, they defined an a-IGZO film as having ordering in
the nearest neighbor distance or the second-nearest neighbor distance of the constituent
atoms, with bonding angle distribution (6). Furthermore, Kamiya et al. concluded that the
amorphous IGZO (a-IGZO) is completely amorphous in its initial state, and that a nano-
sized crystal (nanocrystal, nc) is generated by crystallization during transmission electron
microscope (TEM) observation using a higher electron beam current (7).
In contrast, We have discovered and reported c-axis aligned crystal In-Ga-Zn oxide
(CAAC-IGZO) (8) and nanocrystalline IGZO (nc-IGZO) (9), which have different crystal
morphology from single crystalline and amorphous. These are aggregates of nano–sized
crystals with a width of 1−3 nm and a thickness of 0.7−0.8 nm (pellet structure). In the
cross-sectional TEM observation of CAAC-IGZO, atoms are aligned in the direction
parallel to the substrate surface. In the X-ray diffraction (XRD) analysis, a peak which
indicates c-axis alignment (for example (009) peak at 2θ = 31° in InGaZnO4 film) is
observed, and a-b plane alignment is not observed. In addition, crystal grain boundaries
are not seen in the plan-view TEM observation of CAAC-IGZO (10). Due to its electrical
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ECS Transactions, 64 (10) 155-164 (2014)
Figure 1. Classification of crystalline oxide. (CAAC and nc: discovered by SEL and
mass produced by SHARP. Amorphous-like: Soft and low density containing nc.
Amorphous: Not confirmed by SEL)
CAAC-IGZO and nc-IGZO are fabricated, for example, under the following
conditions:
1. RF or DC magnetron sputtering is used.
2. CAAC-IGZO film can be deposited on a heated substrate and nc-IGZO film can be
deposited at room temperature (R. T.) (as-deposited). Both films are deposited at
high plasma power under high vacuum. An a-like IGZO film is deposited at low
plasma power under low vacuum in R. T.
3. A polycrystalline IGZO target having a cleavage plane between (Ga, Zn)O layers is
used.
4. They can be deposited on the surface of amorphous silicon oxide substrate.
5. To form a high-purity film, mixing H or H2O should be avoided as much as
possible.
For deposition of the CAAC-IGZO film, the substrate temperature was 300°C, the
deposition power was 200 W, the deposition pressure was 0.4 Pa, a mixed gas of Ar and
O2 was used (the proportion of O2 gas flow to Ar+O2 gas flow was 50%).
DC and RF sputtering (13.56 MHz) were performed in the same chamber by
switching the power source. For deposition of the nc-IGZO film, the substrate was at R. T.
and the deposition pressure was 0.4 Pa (high vacuum). The proportion of O2 gas flow to
Ar+O2 gas flow was 100% for DC sputtering and 2% for RF sputtering. The deposition
power was 200 W and 100 W for DC and RF sputtering, respectively.
To observe each cross-sectional structure of the films, thin specimens of the films
were fabricated by ion-milling technique and observed using TEM (JEOL JEM-
ARM200F) equipped with a spherical aberration corrector (Cs corrector) at an
accelerating voltage of 200 kV to obtain HR-TEM images.
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ECS Transactions, 64 (10) 155-164 (2014)
The size in a-b plane direction and the c-axis direction to the substrate were measured
in 30 nano-sized pellets in each sample of the CAAC-IGZO and the nc-IGZO. Here, the
direction to the substrate is expressed as 0° to 90°, when a c-axis was perpendicular (0°)
or parallel (90°) to the substrate, respectively. The results are shown in Table 1. The
average size of pellet structure in the CAAC-IGZO films subjected to substrate heating
does not differ significantly between DC and RF sputtering. That is, the average size of
pellet structure was 1.74 nm (standard deviation σ = 0.39 nm) in the case of DC
sputtering and was 1.73 nm (σ = 0.42 nm) in the case of RF sputtering. Every pellet falls
within the range of 0−30°, which indicates that the c-axis of every pellet structure is
substantially perpendicular to the substrate surface. These results are compatible with the
fact that a stripe contrast parallel to the substrate was observed in the HR-TEM images
(8)(14).
The average size of pellet structure in the nc-IGZO films deposited by DC and RF
sputtering at R. T. was 1.44 nm (σ = 0.41nm) and 1.47 nm (σ = 0.52 nm), respectively,
which is slightly smaller than those of the CAAC-IGZO films. According to the
measurements of 30 points in the film, the direction of nano-sized pellets was to some
extent random, and the directions of a considerable number of nano-sized pellets fell
within 30−60° (27%) and 60−90° (10%).
>
>
DC 200 W
nc 1.44 0.41 2.21 0.65 63 27 10
Tsub. = R. T.
RF 100 W
nc 1.47 0.52 2.42 0.63 7 53 40
Tsub. = R. T.
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ECS Transactions, 64 (10) 155-164 (2014)
2. Having a film density lower but close to that of CAAC, and forming a hard film
also close to that of CAAC
3. Enabling formation of as-deposited crystalline film on a large substrate at R. T.
Next, we checked the following two points: (i) change in the crystallinity of the nc-
IGZO film due to electron beam irradiation and (ii) the initial state of the previously
reported a-IGZO film and the nc-IGZO film. Electron-beam irradiation was performed
using a TEM (Hitachi H-9000NAR), and change in crystal size was observed between,
before and after irradiation. Irradiation with an electron beam of 300 kV was conducted
such that cumulative electron dose reached 7.8 × 108 e−/nm2.
The details of sputtering conditions are shown in Table 2. IGZO films were irradiated
with an electron beam for HR-TEM observation, and change in crystal size was examined.
Among seven samples, a stable film is referred to as an nc-IGZO film (film density,
5.9−6.2 g/cm3), and a film that is changed by electron-beam irradiation is referred to as
an a-like IGZO film (film density is higher than or equal to 5.0 g/cm3 and lower than 5.9
g/cm3).
TABLE II. Density, Hardness, and Change Due to Electron Beam Irradiation in IGZO Films (R. T.
Deposited. Sample 1-6: RF sputtering and sample 7: DC sputtering).
Gas Flow Rate Stability
(sccm) Deposition during
Power Pressure Density Hardness Crystal
Sample Rate Electron
(W) (Pa) (g/cm3) (GPa) Morphology
Ar O2 H2O (nm/min.) Beam
Irradiation
Easy to
1 70 66 1.3 2.5 1.0 1.14 5.05 6.12 a-like
change
Easy to
2 70 98 2 0 1.0 0.24 5.48 6.59 a-like
change
Easy to
3 100 98 2 0 1.0 0.48 5.57 6.72 a-like
change
Easy to
4 200 98 2 0 1.0 1.84 5.85 7.61 a-like
change
5 300 98 2 0 1.0 3.97 5.91 7.77 Stable nc
6 100 98 2 0 0.4 1.78 6.10 7.85 Stable nc
Easy to
7 100 98 2 0 1.0 3.13 5.55 6.71 a-like
change
Sample 6 (high degree of vacuum; deposition pressure, 0.4 Pa) and Sample 5 (high
sputtering power; deposition power, 300 W) were stable even with irradiation at a
cumulative electron dose of 7.4 × 108 e−/nm2 or more, which indicates that they are stable
nc-IGZO films.
Then, we examined initial crystal size in Sample 3 (a-like IGZO) in Table 2, the nc-
IGZO film, and the CAAC-IGZO film, and the changes in size of crystal grains in films
in response to change in cumulative electron dose (Fig.2 and Table 3). A channel region
of back-plane TFT fabricated in commercial product (SHARP, AQUOS PHONE ZETA
SH-02E) was used for the CAAC-IGZO film. We measured 30–40 points. The diffraction
condition or focus position might be misaligned owing to deformation of the film during
electron beam irradiation; therefore, number of points (n) was not a fixed number.
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ECS Transactions, 64 (10) 155-164 (2014)
3.0
2.0
(c)
1.5
(b)
1.0 crystal
CAAC-IGZO
(a) 0.5 nc-IGZO
a-like IGZO
0.0
0.0E+00
0 1.0E+08
1.0 2.0E+08
2.0 3.0E+08
3.0 4.0E+08
4.0 5.0E+08
5.0
- 2 [× 108]
Cumulative electron dose [e / nm ]
Figure 2. Effect of electron beam irradiation on CAAC-IGZO, nc-IGZO, and a-like
IGZO films (Relationship between average crystal size and cumulative electron dose).
The electron beam irradiation was performed until the cumulative electron dose
exceeded 4.0 × 108 e−/nm2. In Fig. 2, the horizontal axis represents the cumulative
electron dose, and the vertical axis represents the average size of nano-sized pellets in a
film observed in a TEM image. The average initial size for the CAAC-IGZO film was
2.18 nm, which are larger than that for the nc-IGZO film. This result shows that the
CAAC-IGZO film is stable even when being subjected to electron beam irradiation. The
nc-IGZO film (deposited at high power under high vacuum) did not change and was
stable.
In contrast, nano-sized crystal grains (0.84−1.82 nm) were included in some part of
the a-like IGZO film (deposited at low power under low vacuum) even in the initial state.
The average crystal size was 1.15 nm, which is slightly smaller than that of crystals
observed in the CAAC-IGZO or the nc-IGZO film in the initial state, and was as large as
several to ten times the size of the minimum unit of the amorphous structure (the distance
between nearest neighbor atoms: approximately 0.2 nm; the distance between second
nearest neighbor atoms: 0.3−0.4 nm) (6)(7). In other words, the completely amorphous
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ECS Transactions, 64 (10) 155-164 (2014)
structure discussed by Kamiya et al. was not observed even in the initial state. The a-like
IGZO film having nano-sized crystals was changed by electron beam irradiation and the
average crystal size doubled from 1.15 nm to 2.64 nm. In addition, measurement showed
that the spot pattern of the a-like IGZO is similar to that of the nc-IGZO in electron
diffraction (9), which indicates the existence of a large number of nc.
As shown in Fig. 2, even an a-like IGZO film deposited under high pressure at low
power has an average crystal size of 1.15 nm in the initial state. InGaZnO4 has a cleavage
plane between (Ga, Zn)O planes (10)(14) and tends to have a nano-sized sandwich
structure of (Ga, Zn)O / InO2 / (Ga, Zn)O; therefore, minimum-sized pellet crystals (Fig.
2(a)) are considered to be formed when separated from the sputtering target and function
as “initial nuclei”. When the pellets are sputtered from the target, they react with In, Ga,
or Zn, which is also derived from the target components and the deposition gas, or oxides
of those elements and grow in plasma generated by magnetron discharge. If the sputtering
power is strong, the growth is promoted by the energy so that an nc structure is formed
(Fig. 2(b)).
A deposition with the use of a highly pure target in a highly pure gas while heating a
substrate forms a CAAC-IGZO film. In the CAAC-IGZO film, like an nc-IGZO film,
nano-sized pellets grow laterally (in a-b plane) to the size of those in the initial state of
the film (Fig. 2(c)) through the reaction with In, Ga, Zn, or their compounds. In contrast
to the nc-IGZO film in which nano-sized pellets are arranged on the substrate randomly,
in the CAAC-IGZO film, nano-sized pellets are uniformly arranged in the lateral
direction and stacked. This is probably because a factor preventing movement of the
nano-siezd pellets, such as H or H2O, does not exist.
Fig. 3 schematically shows the presumed film formation mechanism described above.
At the time of sputtering, not only pellets but also In, Ga, Zn and Oxygen atoms and their
oxides (not shown in Fig. 3) are sputtered, stimulating the growth of initial nucleus
pellets in the width direction.
The greatest characteristic of the CAAC structure formation mechanism is that the
cleavage plane in the structure can lead to the presence of structurally extremely stable
pellet structure, each having a three-layer sandwich structure of (Ga, Zn)O / InO2 / (Ga,
Zn)O, as initial nuclei. As a result, a structure that is different from a known epitaxially
grown film, i.e., a film formed by crystal growth of atoms sequentially arranged on a
substrate, develops.
(A) (B)
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ECS Transactions, 64 (10) 155-164 (2014)
Figure 3. Model diagrams of formation mechanism of (A): CAAC-IGZO film (with heat)
and (B): nc-IGZO film (at R. T.).
In this section, FET characteristics will be discussed; the goal is to explore the
possibility of applying CAAC-IGZO films to LSI. To explore the possibility of FET
downsizing, which is essential in LSI applications, we fabricated 13 CAAC-IGZO FETs
with L/W = 62 nm/59 nm and measured their transistor characteristics. The results shown
in Fig. 4 indicate that the FETs have field effect mobilities of 5–10 cm2/Vs and exhibit
normally-off characteristics.
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ECS Transactions, 64 (10) 155-164 (2014)
Figure 6(A) shows the results of measuring FET leakage currents (transistor off-state
currents) (11). We obtained 6 yA/μm at 85°C, which is an upper temperature limit for
LSI. Figure 6(B) shows a cross-sectional structure of a device using the FET that we
developed. The device has a three-dimensional (3D) complementary metal oxide
semiconductor (CMOS) structure in which an n-type OS-FET is formed over a p-type Si-
FET.
(B) WLIGZO
BL
WLC Cell capacitor IGZO FET PI
Gate
Active GI S / D
layer barrier
barrier
(Floating gate)
Back Gate
Gate
p+Si or n+Si
Si FET(P or NMOS) BOX
Si substrate
Figure 6. (A) Measurement results of extremely low Ioff (relationship between leakage
current and measured temperature), and (B) feasible OS-LSI application: Schematic
diagram of stacked device structure with OS- and Si-FETs.
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ECS Transactions, 64 (10) 155-164 (2014)
Figure 7. Measured results of cutoff frequency with different channel lengths (L).
Conclusion
References
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