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REVIEW ARTICLE

PUBLISHED ONLINE: 23 MARCH 2016 | DOI: 10.1038/NMAT4599

Metal oxides for optoelectronic applications


Xinge Yu1,2, Tobin J. Marks1* and Antonio Facchetti1,3*

Metal oxides (MOs) are the most abundant materials in the Earths crust and are ingredients in traditional ceramics. MO semi-
conductors are strikingly different from conventional inorganic semiconductors such as silicon and IIIV compounds with respect
to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and opto-
electronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO
semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting
oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, pn junctions and complemen-
tary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semi
conductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional
electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and
selected applications in thin-film transistors, solar cells, diodes and memories.

T
he discovery of hydrogenated amorphous silicon (a-Si:H) including wide-gap ionic MOs, represent electronic structure in
exposed new frontiers in large-area electronics1. This semi- reciprocal space, with the conduction band minimum (CBM) and
conductor is a key material for thin-film transistors (TFTs) the valence band maximum (VBM) curvatures and dispersions
used in display backplane electronics; yet, its low carrier mobil- determining the electron and hole effective masses, respectively.
ity (~0.51.0 cm2 V1 s1), optical opacity, poor current-carrying Smaller effective masses mean greater CBM and VBM hybridi-
capacity and modest mechanical flexibility present challenges for zation, affording larger carrier mobilities, all other factors being
future applications. To overcome such limitations, researchers have equal. Note that transport in MOs is very different from that in Si
explored the use of metal oxides (MOs), which, compared with semiconductors, where hybridized sp3 -bonding and sp3 *-anti-
crystalline silicon and other IIIV semiconductors, exhibit unique bonding states define the VBM and CBM, respectively 9. In the
properties, including excellent carrier mobilities even in the amor- oxides of interest here, the VB is typically composed of occupied 2p
phous state, mechanical stress tolerance, compatibility with organic O anti-bonding states, and the CB primarily of unoccupied ns metal
dielectric and photoactive materials, and high optical transpar- bonding states (Fig. 1a)8. The spatially extended, spherically sym-
ency. Furthermore, high-quality electronic-grade MO thin films metrical ns-orbital CBM affords small electron effective masses and
are accessible using vapour- and solution-phase methodologies in efficient electron transport even in the amorphous state, because
near-ambient conditions (~25C under air), widening their appli- the spherically symmetrical metal s-orbital overlap is minimally
cability to high-value products such as inexpensive circuits, and to affected by lattice distortions. In contrast, the spatially directional
flexible organic light-emitting diode (OLED) displays and solar cells Si sp3 states experience dramatically reduced carrier mobilities in
on plastic substrates. the amorphous (a-Si) state. Thus, the electron mobilities of AOSs
The first MO TFT using semiconducting SnO2 was reported in are often similar to those of the corresponding single crystals8, and
1964 (ref.2), yet it was the more recent work by Hosono that stimu- the subgap distributions of the density of states (DOS) between
lated extensive research and increases in performance3. MO TFTs amorphous covalent (such as a-Si) and amorphous oxide (such as
based on polycrystalline MO materials such as indium oxide (In2O3; a-IGZO) semiconductors differ greatly (Fig.1b)9. The subgap DOS
ref. 4), tin oxide (SnO2; ref. 5) and zinc oxide (ZnO; ref. 6) were in a-IGZO is 10100 times smaller than in a-Si:H10,11.
reported. The first amorphous oxide semiconductors (AOSs), whose Many MO (semi)conductors have energy gaps greater than 3eV,
compatibility with large-area fabrication processes make them tech- hence, they are transparent in the visible spectrum. Although from a
nologically appealing, were synthesized in 1954 (ref.7), yet there was traditional band-structure perspective, high conductivity and opti-
little interest in their properties until Hosonos work on InGaZn cal transparency seem contradictory 12; in many (semi)conducting
oxide (IGZO) sparked worldwide attention in 2003 (ref.8). IGZO MOs, strong interactions between the O 2p- and metal ns-orbitals
TFTs have since been commercialized in active-matrix displays, produce a band structure characterized by high free-electron mobil-
joining the widely used transparent conducting oxide (TCO) elec- ity (e) due to the low effective mass and by low optical absorption
trode material, tin-doped indium oxide (ITO). The unique proper- due to the large bandgap (Burstein-Moss shift) and the low DOS in
ties of MOs, their synthesis and their use in optoelectronic devices the CB (ref. 12). However, this unique electronic structure causes
are described in this Review. a dearth of p-type MOs, as hole conduction is hampered by local-
ized O 2p orbitals and deep VBM levels where holes are trapped by
Optoelectronic properties of metal oxides O ions12,13. Band-structure and band-energy modifications are key
Carrier mobility is a key metric of semiconductor performance. strategies for the design of p-type MOs, and electrical, X-ray and
Traditional band theory descriptions of transport in semiconductors, photoemission experiments argue that greater VBM dispersion is

Department of Chemistry and the Materials Research Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. 2State Key
1

Laboratory of Electronic Thin Films and Integrated Devices, School of Opto-electronic Information, University of Electronic Science and Technology of
China (UESTC), Chengdu 610054, China. 3Polyera Corporation, 8045 Lamon Avenue, Skokie, Illinois 60077, USA. *e-mail: t-marks@northwestern.edu;
a-facchetti@northwestern.edu

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REVIEW ARTICLE NATURE MATERIALS DOI: 10.1038/NMAT4599
a
Covalent semiconductors Metal oxides

Crystalline Amorphous Crystalline Amorphous

Oxygen 2p-orbital

sp3-orbital

Metal ns-orbital

b
a-Si:H a-IGZO

CB

CB Hall
Barrier

Tail states Donor


Tail states
level
Localized states

n-TFT
Energy (eV)

Deep levels
Mobility gap

Deep levels
~1.5 eV near surface
Inversion
/p-TFT
Tail states Tail states

VB VB

Log (DOS) Log (DOS)

Figure 1 | Electronic structures of Si and metal oxides. a, Schematic orbital contours for charge transport pathways in the conduction band of crystalline
and amorphous covalent semiconductors (Si) and metal oxides. b, Comparison of subgap DOS in a-Si:H and a-IGZO (different DOS govern n- or p-type
TFT behaviours, donor levels and Hall effect parameters; the barrier is the energy distribution when working in percolation conduction). VB, valence band;
CB, conduction band. Figures reproduced from: a, ref. 8, NPG; b, ref. 9, IEEE.

achievable using metal orbitals with energies close to O 2p or using their chirality (degree of bond connectivity twisting), SWCNTs
more extended anion orbitals, as in CuGaO2 and SrCu2O2 (ref.14). can be semiconducting or metallic; for instance, the bandgap for
In optoelectronic applications, MO semiconductors compete to ~1-nm-diameter SWCNTs is ~1eV similar to that of Si. SWCNTs
some degree with other unconventional semiconductors. The most exhibit extraordinarily high strength and stiffness, and single
promising alternatives include organic semiconductors, carbon SWCNTs can have extremely high hole mobilities (h) and con-
nanotubes (CNTs), and 2D materials such as graphene and MoS2 ductivities. However, these parameters fall significantly in SWCNT
(Table1). Organic semiconductors, both small molecule and poly- network films. Single-tube and CNT network-based devices can be
mer, share a common structural motif of delocalized -electrons fabricated either by vapour phase (typically chemical vapour depo-
and solubilizing substituents (typically hydrocarbons)15. In con- sition, CVD) or solution phase (typically spin-coating) processes.
trast to MO semiconductors, these organics can efficiently trans- Metallic SWCNT films are now commercially available as viable
port holes, electrons or both depending on their structures, and alternatives to metals and MOs, whereas the use of semiconduct-
recent advances include very high mobilities, approaching poly-Si. ing SWCNTs is more limited by process reliability, cost and film
Furthermore, these -organics are easily solution processed to performancestability.
afford stable formulations and inks, with polymers preferred for Graphene is another promising electronic material consisting of
printing. However, these organic solids are bound by relatively weak sp2 carbon atom monolayers with a 2D honeycomb lattice18. Single
intermolecular interactions, so that post-deposition film process- graphene layers are obtained from graphite by simple mechanical
ing has stringent process windows to preserve film continuity and exfoliation, and CVD processes can also be utilized for their synthesis.
morphology. Similar to Si, the largest mobilities are obtained from As for SWCNTs, graphene also exhibits impressive mechanical stiff-
structures forming uniform, contiguous crystalline domains, with ness. Graphene is a gapless semiconductor with high e and electrical
minimum grain boundaries to compromise device metrics and uni- conductivity. However, lack of reliable and cost-efficient production
formity 16. Most -organics exhibit intense optical transitions in the of perfectly structured graphene and the gapless electronic structure
visible, limiting transparency. have to date limited large-scale implementation. Two-dimensional
Single-wall CNTs (SWCNTs) are seamless single-walled gra- layered transition metal dichalcogenides, especially MoS2, have also
phene nanocylinders17 with typical diameters ranging from 0.3 to advanced rapidly 19. MoS2 monolayers not only exhibit good chemi-
70 nm and lengths reaching the centimetre scale. Depending on cal stability, but also unique mechanical and electrical properties

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NATURE MATERIALS DOI: 10.1038/NMAT4599 REVIEW ARTICLE
Table 1 | Comparative metal oxide, silicon, organic, single-wall carbon nanotubes, graphene and MoS2 semiconductor
optoelectronic properties.
Material Polarity Bandgap (eV) Typical growth methods e or h (cm2 V1 s1) Transport type Ref.
Metal oxide p, n* 2.08.0 Sputtering, PLD, thermal 10 10 (single crystal, by vapour phase)
1 2
Band-like 12
evaporation, spin-coating, 103101 (polycrystal or amorphous, by
printing vapour phase, solution)
Silicon p, n ~1.1 CVD, liquid-phase epitaxy, 102103 (single crystal) Band-like (crystalline) 8
spin-coating, printing 101102 (polycrystal) Band-like or hopping
101100 (amorphous) (amorphous)
101102 (solution)
Organic small p*, n 2.54.0 Thermal evaporation, 100101 (single crystal) Band-like (single crystal) 15
molecules spin-coating, printing 105101 (v) MTR (polycrystalline)
105101 (SC) VRH (amorphous)
104101 (Pr)
Organic polymers p*, n 1.52.5 Spin-coating, printing 105101 (SC) MTR (polycrystalline) 15
105100 (Pr) VRH (amorphous)
Single-wall carbon p*, n ~1.0 CVD, spin-coating, printing 106 (maximum, single tube) Ballistic (single tube) 17
nanotubes 101104 (CVD) Percolating in network
101102 (SC) (carbon nanotube films)
101102 (Pr)
Graphene n, p* Absence of CVD, micromechanical 105 (maximum, single sheet) Ballistic (single flake) 18
bandgap exfoliating, spin-coating, 101104 (CVD) Percolation (graphene
printing 101104 (ME) films)
101102 (SC)
101102 (Pr)
MoS2 n, p* 1.31.8 CVD, micromechanical 103 (maximum, single sheet) Band-like 19
exfoliating, spin-coating, 101102 (CVD)
printing 100102 (ME)
100102 (Pr)
*Predominant character. MTR, multiple trapping and release; VRH, variable range hopping; v, vapour phase; SC, spin-coating; Pr, printing; ME, mechanically exfoliated.

approaching high-quality graphene sheets, but with a semiconduct- SnO2 (ref.2) and In2O3 (ref.20) films fabricated by thermal evap-
ing gap. MoS2 monolayers can be obtained by micromechanically oration and sputtering, respectively, were the first MO semiconduc-
exfoliating bulk MoS2 crystals, CVD growth, or solution processing tors used in TFTs, yet they exhibited modest performance (Table2).
and post-annealing. Nevertheless, uniform growth of large-area, In contrast, the enhanced crystallinity of ZnO films grown by
high-quality MoS2 thin films remains challenging. radiofrequency magnetron sputtering at 25C allowed e of about
With respect to these materials, MOs (and AOSs in particular) 1.2cm2V1s1 to be reached21, further improved to e50cm2V1s1
still present clear advantages for optoelectronic applications as by using gate insulators with a high dielectric constant k (ref.22).
a result of the combination of high carrier mobility, good optical In fact, it has been shown that mobility in MOs displays a power
transparency, straightforward synthetic access, large-area electrical law dependence on k (ref. 23). Recently, flexible ZnO TFTs with
uniformity and mechanical flexibility. In the following sections, we e20cm2V1s1 have been fabricated using atomic layer deposi-
focus on MO applications in TFTs (Table2), diodes, memories and tion (ALD) at 90C (ref.24).
photovoltaics (Table3), subdividing the TFT section according to Despite these encouraging results, carrier density in MOs is dif-
their growth methodology (detailed in Box1). ficult to control owing to large numbers of oxygen vacancies25,26;
major advances were achieved when Hosono and colleagues synthe-
Vapour-processed transistors sized IGZO films grown epitaxially on single-crystal yttria-stabilized
TFTs are valves in which charge transport is modulated by apply- zirconia substrates3. High-resolution cross-sectional transmission
ing two independent electrical potentials (Fig. 2a). These three- electron microscopy indicates that the InGaO3(ZnO)5 lattice has
terminal devices have a conducting gate, source and drain electrodes alternating InO2 and GaO(ZnO)5 layers stacked along the (0001)
contacting a semiconductor, and a dielectric insulator layer between direction, similar to ITO and Ga-doped ZnO (Fig. 2b). The film/
the semiconductor and the gate electrode. Charge carriers accumu- substrate interface is atomically flat despite the high-temperature
late under a gate voltage bias, and drift from the source to drain annealing (1,400C), with the lattice mismatch relaxed within a few
electrode. The sourcedrain current scales as the carrier density atomic layers from the interface. Importantly for carrier stabilization,
multiplied by the carrier mobility (), the most significant metric introducing Ga in the GaO(ZnO)5 layers does not generate carriers
in TFTs, and constrains the device operational speed. The current as it not only replaces Zn2+ in the tetrahedral sites, but also occupies
on/off ratio, Ion/off, the threshold voltage (VT) and bias stability are trigonal-bipyramidal coordination sites, thereby maintaining local
additional important TFT metrics. For TFT fabrication, the semi- electroneutrality. The InO2 layers prevent O2 out-diffusion, which
conductor channel layer, the sourcedrain electrodes and the gate would create carrier-generating O vacancies. IGZO TFTs fabricated
insulator layer are deposited using either vapour-phase or solution using ITO source, drain and gate contacts, and an amorphous HfO2
methods (Box1). Although we focus here on MO semiconductors dielectric exhibited e=80cm2V1s1 and Ion/off=106.
(Table2), MOs with more conducting or insulating character can This excellent performance encouraged the exploration of IGZO
also be implemented in every TFT component, including the gate, AOSs, and transparent a-IGZO TFTs were fabricated on plastic
source and drain electrodes, and the gate dielectrics. substrates8. a-IGZO films were deposited at 25C by pulsed-laser

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REVIEW ARTICLE NATURE MATERIALS DOI: 10.1038/NMAT4599

Table 2 | Thin-film transistor metrics for representative vapour- and solution-processed metal oxide semiconductor films.
Deposition Metal oxide Polarity Sourcedrain/ Dielectric Substrate e or h Ion/off Tgrowth/Ta (C) Year Ref.
technique gate (cm2 V1 s1)
Vapour phase
Thermal SnO2 n Al Al2O3 Glass NA NA - 1964 2
PLD IGZO n ITO/ITO Y2O3 PET 7 103 RT/NA 2004 8
ALD ZnO n Au/ITO AHO PET 20.2 107 90/NA 2015 24
Sputtering ZnO n Ti/Au/Si SiO2 Si 1.2 106 RT/NA 2003 21
In2O3 n ITO/Si SiO2 Si 15.3 108 RT/NA 2010 26
IGZO n Au/Si SiO2 Si 73.9 107 RT/150 2009 33
IZO n ITO/Si SiO2 Si 30.4 108 RT/200 (O2) 2013 25
IGZO n Mo SiNx /SiO2 Glass 6.7 109 RT/300 2015 32
SnO p Au/Ti Al2O3 ZrO2 1.3 10 2
500/NA 2008 34
SnO p Ni/Au/IZO Paper Paper 1.3 102 RT/150 2013 35
CuOx p Au/ITO ATO Glass 0.01 104 RT/NA 2014 38
Solgel chemistry
Spin-coating In2O3 n Au/Si SiO2 (SAND) Si 0.7 (43.7) 106 400/NA 2008 43
ZnO n Zn/ITO ATO Si 5.25 105 500/NA 2007 41
IZO n W/Si SiO2 Si 11.4 108 250/NA 2011 47
IGZO n IZO/Ti/Au Al2O3 PAR 3.77 108 RT/NA 2012 49
IZO n ITO/ITO Al2O3 Polyimide 4.03 109 250/NA 2013 46
ZnO n Al/Si SiO2 Si 10 10 7
180/NA 2013 42
IGZO n Al/Si SiO2 Si 10.1 105 400/NA 2013 48
QSL n Al/Al Al2O3 /ZrO2 Glass 40 104 200/NA 2015 50
CuOx p Ni SiO2 Si 0.29 104 700 (vacuum)/NA 2015 59
Ink jet IGZO n Ti/Au/Si SiO2 Si 10.5 105 Light irradiation 2015 54
Gravure IGZO n Mo/Ti SiNx Glass 0.81 106 550/NA 2010 55
In2O3 n Al/Au Al2O3 PI 8 106 300/150 2015 56
IZO n ITO/Si SiO2 Si 9.1 106 425/NA 2015 57
Aerosol-jet printing ZnO n Au/Cr/ Iongel Kapton 1.6 105 250/NA 2013 58
PEDOT:PSS electrolyte
Spray pyrolysis
Spray ZnO n Al/Si(Al/Al) SiO2 (SAM) Si 15 (7.6) 106 (103) 400/NA 2009 60
CuOx p ITO/Au/Si SiO2 Si 103 103 275/NA 2013 61
Combustion
Spin-coating In2O3 n Al/Al Al2O3 AryLite 6.0 103 200/NA 2011 62
IYO n Al/Si ZrSAND Si 5.0 10 5
250/NA 2012 63
IYZO n Al/Si SiO2 Si 2.37 107 300/NA 2013 65
IGZO n Al/MoW SiO2 Glass 1.4 106 350/NA 2013 64
IGZO n Al/Si SiO2 Si 5.43 108 300/NA 2013 65
ILO n Al/Si SiO2 Si 9.7 107 300/NA 2015 66
Spray In2O3 n Al/Al Al2O3 AryLite 11.0 104 200/NA 2015 68
IGZO n Al/Si SiO2 Si 7.53 107 300/NA 2015 68
Pre-formed ZnO n ITO/IZO Al2O3 Glass 96 106 Thermal growth 2007 72
nanostructures
CuOx p Au/Si SiO2 Si 15 102 500/NA 2009 73
ZnO n Al/Si SiO2 Si 1.75 108 250/NA 2013 76
ATO, antimony tin oxide; AHO, aluminum hafnium oxide; Tgrowth, film growth temperature; Ta, post film-deposition annealing temperature; NA, not applicable or not reported; QSL, quasi-superlattices of structure
In2O3Ga2O3ZnOGa2O3In2O3; SAM, self-assembled monolayer; RT, room temperature; IYZO, indium yttrium zinc oxide; ILO, indium lanthanum oxide; SAND, self-assembled nanodielectric; PAR, polyarylate.

deposition (PLD) using a polycrystalline InGaZnO4 target, yielding IGZO film depends on carrier concentration, and the two values
a In:Ga:Zn=1.1:1.1:0.9 elemental composition. These films are sta- converge to ~10cm2V1s1 at high carrier densities. Mechanically
ble up to 500C in air and have an optical bandgap of 3.0eV sim- flexible a-IGZO TFTs on polyethylene terephthalate (PET) achieved
ilar to crystalline IGZO (3.4eV). The a-IGZO carrier concentration e=69cm2V1s1.
is tunable from 1014 to 1020cm3 by varying O2 partial pressure from The use of radiofrequency sputtering to fabricate a-IGZO
7to 0.1Pa (Fig.2c). The Hall mobility of amorphous and crystalline TFTs has allowed the intrinsic limitations of PLD in terms of area

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NATURE MATERIALS DOI: 10.1038/NMAT4599 REVIEW ARTICLE
Table 3 | Applications of representative metal oxide materials in microelectronics, including transparent conducting oxides, diodes,
random access memories, solar cells and organic photovoltaics.
Application Metal oxide Deposition technique Performance parameters Processing temperature (C) Year Ref.
pn junction
Diodes CuCrO2:MgZnO PLD ID = 7 mA (2 V) RT (laser annealing) 2008 80
Sensors WO3SnO2 Solgel NO2 200 ppm 200 2010 82
ZnOSnO2 Solgel C2H5OH 200 ppm 300 2007 85
ZnOSnO2 PECVD CO 100 ppm 350 2011 84
Solar cells Ga2O3Cu2O PLD PCE = 5.38% RT 2013 88
Cu2OTiO2ZnO Vapour + ALD PCE = 0.39% 1,140 (HP O2) 2014 89
(nanowire)
Random access CuxO ECP RHS /RLS = 103 NA 2009 91
memories
ZrO2 Solgel RHS /RLS = 102 600 2009 93
NiO Sputtering RHS /RLS = 103 300 2009 92
Transparent conducting ITO Sputtering =104 cm RT 2010 12
oxides
AZO Sputtering =104 cm RT 2010 12
IZO Sputtering =104 cm RT 2010 12
GZO Sputtering =104 cm RT 2010 12
ZITO Sputtering =104 cm RT 2010 12
Organic photovoltaics
Electrode ITO Commercial Rs = 5 sq.1, PCE = 0.39% NA 2013 103
InCdOITO IAD Rs = 4.9 sq.1, PCE = 1.14% RT 2010 105
ZITO PLD Rs = 17.5 sq.1, PCE = 7.41% RT 2014 106
Interfacial layer MoO3 Thermal evaporated PCE = 3.33% NA 2006 111
V2O5 Thermal evaporated PCE = 3.10% NA 2006 111
ZnO Solgel PCE = 10.6% 150 2013 77
NiO PLD PCE = 5.16% RT 2008 107
TiOx Solgel PCE = 4.1% 150 2007 124
GZO, gallium-doped zinc oxide; ID, drain current; , resistivity; AZO, aluminum zinc oxide; PECVD, plasma-enhanced chemical vapour deposition; ECP, electrochemical plating; IAD, ion-assisted deposition; HP,
high pressure; RHS, high resistance state; RLS, low resistance state. See the main text and Table 2 for other definitions.

deposition to be overcome27. Additional device issues, such as bias and inverters (gain ~4.9V/V). Besides SnOx, CuOx is interesting due
stress stability, light sensitivity and long-term operational stabil- to its high Hall h; ~100cm2V1s1 was achieved because the tetra-
ity, were addressed by post-deposition and fabrication thermal hedral coordination of oxide ions in CuO2 reduces the localization
annealing 28, encapsulation29 and plasma treatment 30. According to of the O 2p-dominated VB. However, obtaining high-performance
DOS modeling 31, these processes suppress charge trap densities CuOx TFTs remains challenging, due to large hole effective masses
in a-IGZO, especially tail states near the CBM, thereby enhanc- and deep VBM levels, and difficulties in controlling hole densities.
ing stability. Furthermore, exposing the source and drain contact Thus, although high-quality CuOx films can be grown by PLD on
areas of sputtered a-IGZO films to ultraviolet irradiation dramati- MgO at 850C, the resulting TFTs exhibit h of only 0.26cm2V1s1
cally reduces the contact resistivity from 106 to 105cm (ref.32). (ref. 36). Low-temperature CuOx sputtering deposition followed
Nowadays, sputtering is the preferred industrial process for a-IGZO by slow post-annealing at 200C yielded high film crystallinity, yet
growth in TFTs for OLED display backplanes. By controlling the the TFT performance remained poor (h103cm2V1s1)37. More
process parameters, including O2 partial pressure, growth pres- recently, transparent p-type TFTs were fabricated on glass sub-
sure, target composition, film thickness and annealing tempera- strates using CuOx films sputtered at 25C with h0.01cm2V1s1
ture, a-IGZO TFTs processed at 150C achieve e=73.9cm2V1s1 (ref. 38). These data show that useful MO h values are far from
(ref.33). Beyond a-IGZO TFTs, other MOs are also being investi- being achieved yet.
gated (Table2), aiming at achieving the stability and performance of
a-IGZO with simpler compositions. Solution-processed transistors
All the aforementioned oxides are n-type semiconductors. To Transitioning film growth from capital-intensive vapour-phase to
date, few p-type MOs have been reported as a result of the afore- solution-phase technologies is of paramount importance for MO
mentioned localized O 2p-dominated VB and high densities of optoelectronics. Indeed, the possibility of fabricating films from liq-
deep traps near the VB. Epitaxial SnOx on (001) yttria-stabilized uid precursors in ambient conditions holds great attraction for MOs
zirconia at 500 C yielded the first p-type oxide TFT exhibiting versus Si, nitride and chalcogenide semiconductors. Progress here
h1.3cm2V1s1 (ref.34). SnOx p-type TFTs sputtered on paper has been impressive (Table2), opening possibilities for MO printing.
substrates at 150C also afford h>1cm2V1s1 (ref.35), which
were combined with n-type a-IGZO TFTs to demonstrate CMOS Solgel. In typical solgel processes, MO precursor solutions are
(complementary metal-oxide semiconductor) differential amplifi- prepared by dissolving metal salts in a solvent, typically H2O with a
ers (gain ~4.1V/V), common source amplifiers (gain ~16.3V/V) stabilizing agent39. The resulting coordinated metal species undergo

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Box 1 | Oxide growth techniques.

Metal oxides films can be deposited using vapour- and solution- complex and large-area substrates. ALD processes are typically
phase techniques12,13 as summarized below. used to manufacture high-quality MO dielectric films.

Vapour-phase processing. There are four main vapour-phase Solution-phase processing. There are three main solution-phase
techniques for depositing MO films. techniques for depositing MO films.

Thermal deposition. Thermal evaporation uses a volatile source Spin-coating. Spin-coating is a simple method for depositing opto-
material under high vacuum to grow films on a substrate of electronic films, generally on planar substrates. A precursor solu-
interest, and is widely used to manufacture metallized products. tion is applied on the substrate surface, fixed by suction to a holder,
MO film thermal deposition faces several challenges, including: which is either spinning at low speed or stationary. Next, the sub-
(i) post-deposition O content adjustment is required to achieve strate is rotated at high speed to spread the coating material by
the desired composition, owing to O2 loss during MO evaporation; centrifugal force, coating the substrate with a thin film. Film thick-
and (ii) high substrate temperatures are necessary to optimize ness and quality depend on the acceleration and spinning speed
reactions between ionized species on the substrate, and common as well as the solution and solvent viscosity, volatility and concen-
plastic substrates are not compatible with high growth rates. tration. Spin-coating is widely used in oxide film microfabrication
using solgel precursors and in integrated circuit fabrication to
Sputtering. Sputtering is a common technique for depositing MO deposit photoresist layers.
(semi)conductors. Most utilized is magnetron sputtering where
magnets behind the target enhance bombardment by ionized Spray coating. Also known as spray pyrolysis, spray coating is
gases, increasing growth rate and film uniformity. Advantages another simple, inexpensive deposition method for electronic
of sputtering include: (i) film growth near room temperature; materials, compatible with large-area growth on plastic. Films are
(ii)compatibility with thermally sensitive substrates, such as plas- typically grown by aerosol spraying precursor solutions onto pre-
tic foils; and (iii) control of MO film morphology, composition heated substrates, where the constituents undergo chemical reac-
and carrier concentration via the deposition parameters, such tion. These chemical reagents are selected such that all reaction
as O2 pressure and sputtering power. Sputtering is widely used products are volatile at the deposition temperature. Spray pyro
industrially for metal and MO depositions. Nevertheless, it is lysis is particularly useful for MO depositions, and is a commercial
costly due to the specialized equipment and targets, especially for method for fabricating transparent electrical conductors on glass.
large-areagrowth. Spray pyrolysis film roughnesses are typically inferior to those
of spin-coated films, but can be optimized by adjusting process
Pulsed-laser deposition. PLD is also an efficient flash-evaporation parameters. Spray pyrolysis requires low viscosity solutions, which
technique where a MO or other target is irradiated with a high- restricts the solvent selection.
power pulsed ultraviolet laser beam, vapourizing the target mate-
rial in a plasma plume and depositing it as a thin film. This process Printing. Printing is an additive process involving simultane-
can occur in vacuum or in a background gas, such as O2, which is ous film deposition and patterning, typically at low tempera-
commonly employed in MO film growth. PLD affords high-qual- tures, thereby minimizing chemical and energy consumption.
ity and high-performance films with well-controlled compositions Furthermore, printed pattern shapes and sizes can be readily
and morphologies. However, it is seldom applicable to production modified without process redesign. The most utilized electron-
scales because of limitations in large-area film uniformity, low ics printing techniques are ink-jet, aerosol jet, gravure, flexo and
deposition rates and high capital costs. screen printing; note that screen printing is used industrially
to create metal lines. Impressive advances have been made in
Atomic layer deposition. ALD films are grown by exposing the printing organic and MO electronic materials; however, imple-
substrate to alternating pulses of gaseous reagents that undergo mentation issues at the industrial scale include enhancing for-
self-limiting chemical reactions. In contrast to chemical vapour mulation stability, broadening process windows, and enhancing
deposition, the reagents are never present simultaneously in the film uniformity. Furthermore, for applications such as circuits,
reactor, but are inserted as a series of sequential, non-overlapping resolution and registration must achieve acceptable yields in
pulses, resulting in atomic-scale growth. Varying the cycle num- production. For MOs, high-temperature post-annealing is
ber enables uniform growth with high precision on arbitrarily typically required.

hydrolysis forming hydroxides, which slowly convert to colloidal To lower the processing temperature, the same precursor solu-
solutions (sol), and eventually to integrated MO networks (gel) con- tions were used for spin-coated ZnO films, which were then post-
taining liquid and solid phases. For TFTs, films are cast from the sol annealed at 500 C. Remarkable e up to 5.25 cm2 V1 s1 with
precursors, which are then thermally annealed to condense the lat- Ion/off=105 was achieved with AlTi oxide dielectrics and vacuum-
tice and remove volatile organics. TFTs using MO films including deposited Zn contacts41. Subsequently, ammonia-based carbon-free
In2O3, IGZO, zinc tin oxide (ZTO), indium gallium oxide (IGO), precursor solutions yielded ZnO TFTs with a e 11 cm2 V1 s1
indium zinc oxide (IZO), and ZnO semiconductors, Al2O3, ZrO2, with 180Cprocessing 42.
HfO2, Ta2O5, Y2O3 dielectrics, and ITO, In2O3 and F-doped ITO Although less crystallizable than ZnO, In2O3 is an ideal
conductors have been fabricated by solgel processing. solgel TFT candidate, and In2O3 film growth was achieved by
Among MO TFT semiconductors, solgel ZnO TFTs were first spin-coating solutions of ethanolamine (EAA) and InCl3 in meth-
fabricated by dip-coating Si or SiO2 substrates in zinc acetate oxyethanol, varying the EAA:In3+ ratio from 0.0 to 15 (Fig. 3a)43.
propanol or diethanolamine solutions, followed by 900 C EAA strongly affects crystallization, with optimal performance
annealing 40. The resulting devices exhibited Ion/off 103 and trans (e=43.7cm2V1s1) achieved for EAA:In3+=10and Tal=400C.
conductance gm 0.6 S, with no other TFT metrics reported. The post-deposition temperature for solgel MO films can be

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NATURE MATERIALS DOI: 10.1038/NMAT4599 REVIEW ARTICLE
a b c
InO2 layer
00021
Ga(ZnO)5+

Hall mobility (cm2 V1 s1)


block 0000 101
S l
sta
D
In le cry
Semico ing
nducto Os
r

5.7 nm
Zn/Ga IGZ
Dielectr O
ic
Gate
ate

1.9 nm
[0001] ub str
Zs Amorphous films
YS 40 nm
Single-crystal films
[1100] 0
10
1015 1016 1017 1018 1019 1020 1021
Carrier concentration (cm3)

Figure 2 | Vapour-phased metal oxide and thin-film transistor. a, Device architecture of a bottom-gate top-contact thin-film transistor. S, source
electrode; D, drain electrode. b, Crystal structure schematic (left) and high-resolution transmission electron microscopy lattice image (right) of
InGaO3(ZnO)5. YSZ, yttria-stabilized zirconia. c, Plot showing the relationship between 25 C Hall mobility and carrier concentration for a-IGZO films
versus single-crystal InGaO3(ZnO)5 films. Figures reproduced from: b, ref. 3, AAAS; c, ref. 8, NPG.

reduced by modifying the thermal treatment conditions (performed Solgel methods are particularly attractive for their compat-
under O3 (ref.44), with controlled O2 pressure45 or in vacuum46) or ibility with printing processes for the fabrication of MO TFTs
with specialized precursors. For instance, it has been suggested that and other optoelectronic devices51,52. The first ink-jet printed
additional vacuum annealing at 5102Torr and at temperatures IZO TFT was achieved53 using aqueous InCl3 + ZnCl2 solutions
lower than 200C facilitates In2O3 solgel condensation, achieving printed on SiSiO2 substrates, reaching e=7.4cm2V1s1 after
e2.62cm2V1s1 (ref.46). 400 C annealing. Recently, ink-jet printed a-IGZO TFTs, with
As with vapour deposition, binary and ternary MO solution e 10.1 cm2 V1 s1 after intense pulsed white light irradiation
processing was also explored. A low-temperature solgel on chip (100Jcm2) were demonstrated54. Gravure printing of Zn(C2H3O2)2,
route to a-IZO and a-IGZO TFTs (Fig. 3b) was recently demon In(NO3)3 and Ga(NO3)3 inks was also used to fabricate a-IGZO
strated, where an In alkoxide cluster, Zn(OCH2CH2OCH3)2, and TFTs exhibiting e = 0.81 cm2 V1 s1 after 550 C annealing 55.
Ga(OCH(CH3)2)3 in methoxyisopropanol + 2-methoxyethanol Recently, gravure- and flexo-printing In2O3 (using In(NO3)3 pre-
were spin-coated and annealed under controlled humidity to cursor ink), and a-IZO (using In(C4H6NO3)3+ Zn(C4H6NO3)2 inks)
enhance hydrolytic film densification47. Amorphous, high-mobility TFTs were also demonstrated, with e=8cm2V1s1 after 300C
films were optimized using a In/Zn ratio of 7:3 (Fig.3c). The effects annealing 56, and e=9.1cm2V1s1 after 425C annealing, respec-
of processing atmosphere (dry or wet) and annealing temperatures tively 57. Note that the ultrahigh capacitance and compatibility with
were also explored, revealing that wet annealing afforded the high- printing processes of iongel electrolytes make them good can-
est mobilities (e=712cm2V1s1 on SiO2), near-0.0V turn-on didates as dielectrics for low-voltage MO TFTs. Thus, aerosol-jet
voltages and minimal hysteresis (<1.2V). a-IGZO TFTs with low TFT printing of semiconducting ZnO (Zn(NO3)2 precursor ink)
Ga content (5%) annealed at 275 C also afforded good perfor- and electrolyte dielectrics afforded e=1.6cm2V1s1 after 250C
mance with e=4.056.12cm2V1s1, although such devices were annealing 58. However, high-temperature annealing (500C) leads
operationally unstable due to the incomplete hydrolysis of the to significantly better performance (e=12.9cm2V1s1) for all-
Ga alkoxide precursor. More recently, formamide incorporation printed a-IZO TFTs59;,hence, further work is needed to make this
(0100vol%) in IGZO precursor solutions yielded a higher a-IGZO technology compatible with inexpensive plastic substrates.
TFT e, ~10.1 cm2 V1 s1 on SiO2 and 50 cm2 V1 s1 on high-k The availability of solgel p-type MOs has lagged far behind
aluminum zirconia oxide (AZO) at an annealing temperature of n-type MOs. To our knowledge, the first p-type solgel Cu2O TFT
400C (ref.48). was only recently achieved, with h=0.16cm2V1s1 obtained using
To further lower the annealing temperatures, precursor decom- a Cu(OAc)2 precursor solution and a two-step 700C annealing pro-
position at ~25C by deep-ultraviolet irradiation of the deposited cess, first under N2 then under O2, which is essential for optimum
MO films was investigated49. Exposure under N2 to deep-ultraviolet film morphology and p-type operation. Recently, one-step annealed
light promoted M-O-M lattice densification in IGZO films prepared (600C at a O2 partial pressure of 2106Torr,) CuOx TFTs were also
using a Zn(C2H3O2)2 + In(NO3)3, + Ga(NO3)3 solution, and com- demonstrated59, yielding p-type TFTs with h0.29cm2V1s1. The
position and microstructure comparable to 350C annealed films paucity of p-type MOs suggests a challenging research opportunity.
were obtained. This approach was used to fabricate a-IGZO TFTs on
plastic substrates (Fig.3f) with e as high as ~7cm2V1s1. Positive- Spray pyrolysis. Pioneering ZnO studies revealed the potential
gate-bias TFT stress tests show excellent operational stability with- and versatility of this technique for high-performance MO devices.
out film passivation, and a small VT shift of 1.12 V after 10,000 s ZnO TFTs were fabricated at temperatures as low as 200 C by
gate-bias. spray coating aqueous zinc acetate or methanol solutions, achieving
Metal-oxide heterostructures combining two or more MO lay- e ~0.1cm2V1s1, which increases to ~15cm2V1s1 with 400C
ers have been recently implemented in TFTs. Unlike conventional processing 60. Furthermore, low-voltage ZnO TFT operation was
single-channel-layer MO TFTs, these TFTs used spin-coated achieved by integrating spray-coated ZnO films with high-k gate
In2O3Ga2O3ZnOGa2O3In2O3 quasi-superlattices (QSLs)50. The dielectrics, and a low-voltage (<2 V) unipolar MO inverter was
performance of these transistors is not limited by the individual fabricated with two TFTs. Other n-type compositions and condi-
semiconductor bulk carrier mobilities, but is instead dominated by tions were recently explored (Table2). The only spray-coated p-type
the heterointerface structural and electronic properties within the TFTs were fabricated by spraying aqueous Cu(OAc)2solutions on
QSL. QSL TFTs processed at 200 C show e > 40 cm2 V1 s1, far SiSiO2 substrates at 275 C (ref. 61). These CuOx TFTs exhibit
exceeding those of single-layer devices. h104103cm2V1s1.

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REVIEW ARTICLE NATURE MATERIALS DOI: 10.1038/NMAT4599
a b c d
2ME O
InCl3 + EAA In O O
400 C 2 3 O In O
O In O 16 80
InOOH (222) (004)
O In O In O 70
O O 14
10.0

VG hysteresis ID at = 10 nA
O In O Zn-rich Amorphous 60
12 Combustion

Mobility (cm2 V1 s1)


0.0 20
O
15.0 10

Energy
12.5 O O 8
10.0 Zn In-rich
6 10
7.5 O O Solgel
5.0 4
1.0 2
0.0
O Ga O 0 0
20 25 30 35 40 45 O 0 20 40 60 80 100 Reaction coordinate
2 () In2O3 fraction (%)

e f
1 1
10 10 101
Mobility (cm2 V1 s1)

101 101 L = 520 m W = 100200 m


101
IZO IZO
103 103 IGZO
Al2O
3

Ti/Au Ti/Au
103
105 105
PAR su
bstrate
NA NA NA
In2O3 ZTO IZO
107 107 105
200 300 400 200 300 400 200 300 400
Temperature (C) Temperature (C) Temperature (C)

Figure 3 | Solution-processed metal oxide. a, X-ray diffraction-derived microstructure evolution for various In2O3 films fabricated with different
In:ethanolamine (EAA) molar ratios (indicated as mol%). Black scans are SiSiO2 substrates; red scans are Siself-assembled nano-dielectric substrates.
ME, methoxyethanol. b, Metal oxide precursors used in the solgel on a chip process: indium alkoxide cluster, zinc-bis-methoxyethoxide and gallium-
tris-isopropoxide. c, Mobility and gate voltage (VG) hysteresis variations versus In2O3 atomic fraction in IZO TFTs. d, Energetics of combustion synthesis-
based film growth versus the conventional solgel process (top) and the combustion synthetic chemistry (bottom); the red arrows define the input energy
required for M-O-M formation. e, Mobility versus annealing temperature for the indicated metal oxide-based TFTs (In2O3, ZTO and IZO) using combustion
(red) and solgel (blue) synthesis. NA, data not available. f, Optical images and a schematic cross-section of photo-annealed IGZO TFTs and circuits
on polyarylate (PAR) substrates. L, channel length; W, channel width. Figures reproduced from: a, ref. 43, American Chemical Society; b,c, ref. 47, NPG;
d,e, ref. 62, NPG; f, ref. 49, NPG.

Combustion synthesis. An alternative route to lowering solution- to other semiconductors, including indium yttrium oxide (IYO),
deposited MO film processing temperatures is combustion synthe- IGO, ZnO, IGZO, indium yttrium zinc oxide (IYZO), and indium
sis, where fuel and oxidizer pairs imbue MO precursor solutions lanthanum zinc oxide (ILZO)6365. Here a-IXZO (InXZnO,
with large internal energies. This creates self-generated exotherms X = Ga, Sc, Y, La) compositions clarified how metal X stabilizes
within MO films versus conventional, highly endothermic solgel amorphous phases and/or acts as an O getter to optimize carrier
condensations. After precursor deposition and minimal heating concentrations and bias-stress stability. MO combustion synthesis
to initiate combustion, the self-generated, localized heat drives has now been reported by several groups (Table2), demonstrating
M-O-M lattice formation and densification (Fig.3d). its generality. To better understand amorphous phase transport in
The first combustion experiments demonstrated In2O3, a-IZO, such films, combustion-derived InXO materials were prepared for
and a-ZTO films fabricated at temperatures as low as 200 C X=Sc, Y, and La. The results show that cations with radii larger than
(ref.62), with redox-based urea or acetylacetone fuel and M(NO3)x In(iii) induce amorphous character and achieve high e at very low
as chemical precursor fueloxidizer pairs. For TFT fabrication, such X concentrations (~5% for La). Furthermore, increased ionic radii
combined solutions were spin-coated on doped-SiSiO2 substrates, correlate with broader tail-state trap distributions in the trap-limited
the resulting films annealed at 200400C and the process repeated conduction regime, and with greater potential barrier heights in the
until ~2030nm MO films were achieved; finally, Al sourcedrain percolation regime. These results agree well with local structure
contacts were deposited on top. The advantage of combustion syn- information determined from ab initio molecular dynamics simu-
thesis is evident by comparing solgel-derived and combustion lations66. Interestingly, by combining combustion-processed IGZO
synthesis MO TFT performance. In fact, processing In2O3 films with a sorted p-type CNT network, antiambipolar heterojunction
by combustion at 200 C yielded TFTs with e1cm2V1s1 (on circuits based on two TFTs and one resistor have been recently dem-
SiSiO2), whereas solgel TFTs are inactive (Fig.3e). Similar trends onstrated67, whereas in conventional Si-integrated communications
hold for the other MO semiconductors, with results understandable at least seven TFTs are required to create such circuits.
in terms of improved film morphology and composition evolution Recently, a versatile new growth process combining spray coat-
with annealing temperature. Furthermore, In2O3 TFT e increases ing with combustion synthesis (SCS, spray combustion synthesis)
to ~40cm2V1s1 for an annealing temperature of 250C using a was reported68. The combined internal combustion heat and spray-
higher-k gate insulator. This approach was subsequently expanded suppressed gaseous by-product trapping during film growth yields

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NATURE MATERIALS DOI: 10.1038/NMAT4599 REVIEW ARTICLE
a b
8

6 CuCrO2:Mg 100 nm
ZnO 100 nm
4 ZnO:Al 200 nm
Cathode
2

Current (mA)
n-type met Glass substrate
al oxide
p-type met 0
al oxide
Anode 2 In situ laser
annealing
4 Without
annealing
6 Postthermal
annealing
8
3 2 1 0 1 2 3
Applied voltage (V)

c d
50

40
Reset
Top electr
Percentage (%)
ode 30 Set
Metal oxid
e
20
Bottom el
ectrode

10

0
0.5 0.0 0.5 1.0
Voltage (V)

e f
Organic junction e-IFL
h-IFL
(photoactive layer)

1
MoO3

2
V2O5

Top electr Ca
ode 3
Interfacia
l layer 4 Al
ITO Cu
Organic ju
Energy (eV)

nction 5 Au

Interfacia 6
PEDOT:PSS

NiO

l layer
TCO 7
OMe
8
In2xGaxO3
Cr2O3

O
9
Cu2O
ZnO
TiO2

10 C6H13

Ga22xZnxSnxO3
S
n
P3HT
PCBM

Figure 4 | Metal oxide electronics. a, Schematic of a pn junction device. b, Currentvoltage characteristics of a ZnO(n)ZnO:Al(p) diode (inset)
processed under the indicated conditions. c, Random access memory schematic. d, Distribution of the set and reset voltages for d.c. sweep in a
TiNZrO2Pt memory cell stack. e, Schematic of an organic solar cell. TCO, transparent conducting oxide. f, Energy-level schematic depiction for selected
organic solar cell materials and metal oxide electron and hole interfacial layers (e-IFLs and h-IFLs). The grey, light blue and red colours represent work
functions, lowest unoccupied molecular orbital (LUMO) levels and highest occupied molecular orbital (HOMO) levels, respectively. The dark blue and
dark red regions indicate the energy range for LUMO and HOMO levels, respectively, which depends on the metal oxide composition. Dashed lines are
guides for the eyes. Figures reproduced from: b, ref. 80, Elsevier; d, ref. 93, AIP.

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REVIEW ARTICLE NATURE MATERIALS DOI: 10.1038/NMAT4599
ultra-high-quality, dense (by positron annihilation spectroscopy (ReRAMs) and floating-gate TFT flash memories (Fig.4c). So far,
and X-ray reflectivity) In2O3, IZO and IGZO films in remarkably several MOs have been employed in ReRAMs, with an oxide layer
short growth times. SCS produces ~50nm a-IGZO films (minimal sandwiched between two electrodes. Key performance metrics are
thickness for commercial applications) in ~30min, with TFT per- the programming set and reset voltages Vset and Vreset, respectively,
formance far superior to spin-coated combustion films (requiring and the low-resistance state/high-resistance state ratio90. In 2008,
4h growth times) and with comparable mobility, defect densities a ReRAM with an Al electrode on top of CuOxCu (MObottom
and VT shift (~1V) to sputtered films. electrode) was demonstrated, exhibiting programming voltages
Vset=3V, Vreset=1V, and a resistance ratio >103 (ref.91). ReRAM
Pre-formed nanostructures for transistors switching speeds also depend on the memory element size, so scal-
Besides films, MO nanomaterials have been used in TFT channels. ing down device sizes can increase performance. In another study,
Oxide nanostructures show large carrier mobilities, yet control- 100nm100nm ReRAMs were fabricated with ALD-grown NiO
ling the density and orientation of these nanostructures on a large as the MO and Pt electrodes, and exhibited Vset1.5V, Vreset0.6V,
scale is challenging. The most successful TFTs employ ZnO, SnO2 and a resistance ratio of ~102 (ref.92). ReRAMs using solgel ZrO2
nanocrystals, and In2O3 nanowires and nanoribbons6971. TFTs based annealed at 600C, exhibit Vset0.8V, Vreset0.5V, and a resist-
on transparent In2O3 and ZnO nanowires spin-coated on PET have ance ratio of >10 (Fig.4d)93. Also, nonvolatile resistance switching
e>500cm2V1s1 and ~100cm2V1s1 (Ion/off106), respectively 72. was achieved using sputtered ZnO with ITO electrodes on plastic
Remarkably, p-type CuOx nanowires thermally grown on Cu foil (polyethersulfone) substrates, demonstrating transparent flexible
at 500 C and then transferred to SiSiO2 substrates73, yield TFTs ReRAMs with Vset 1.5 V, Vreset 0.5 V, and a resistance ratio of
with h15cm2V1s1. Advances have also been made in moving ~102 (ref.94).
from single-wire devices to nanomaterial networks. For instance, Flash memories are the most common memory configura-
ZnO nanorod TFTs with e 0.6 cm2 V1 s1 were fabricated by tion due to their excellent compatibility with the CMOS circuitry
hydrothermal growth, immersing spin-coated ZnO nanorod films used to address each memory cell, and show reliable and uniform
in aqueous Zn(NO3)2 at 90C (ref.74). Similarly, a ZnO nanowire memory characteristics, fast switching and non-destructive read-
network was fabricated with spin-coated ZnO quantum dots as out. In the most common flash memories, charge storage relies
seeds, followed by immersion in aqueous Zn(NO3)2 for nanowire on trapped charge carriers in a floating gate within the SiO2 or
network growth at <140 C (ref. 75). The resulting TFTs exhibit SiNx gate dielectric, or in a non-conductive discrete trapping layer.
e=0.2cm2V1s1, but suffer from grain boundary effects. Spin- MO materials are suitable for memory devices as non-conducting
coated ZnO nanoparticles treated with Zn(NO3)2 solutions afford trapping layers in the dielectric or in the TFT channel95. In 1995, a
higher e, ~1.75cm2V1s1 (ref.76). MO memory TFT was created with PLD-grown perovskite semi-
conducting (La1.99Sr0.01CuO4) and dielectric ((Pb,La)(Zr,Ti)O3)
pn junction devices layers. These devices can be written and erased at 7V with a pulse
Diodes can be fabricated by combining p- and n-type MO layers to width of less than 1 ms (ref. 96). Recently, solution-processed
form pn junctions (Fig.4a). A conducting anode, a semiconductor TFT-based memories were fabricated with spin-coated MO
pn junction and a conducting cathode achieve rectifying current semiconductor channels (In2O3, IGO) and a solution-processed
voltage characteristics, for applications such as diode rectifiers, sen- Cu-doped zirconia (CuZrOx) composite acting as an electro-
sors and solar cells. However, MO pn junctions are rare due to the chemical redox trapping layer within the gate dielectric97. Using
limited selection of p-type MO semiconductors. The demonstra- a high-capacitance self-assembled nanodielectric layer, these TFT
tion of p-type CuAlO2 films by PLD growth77, followed by p-type memories demonstrated e2.5cm2V1s1, good reliability and
CuGaO2 (ref.14) and SrCu2O2 (ref.78) film growth, led to the first operation below3V.
MO pn junction diode in 2000. Such a device was composed of a
sputtered SrCu2On+ZnO bilayer and ITO electrodes, and exhibited Organic solar cells
a rectification ratio of ~80 from 1.5to 1.5V (ref.79). In 2008, a Organic photovoltaic (OPV) cells are excitonic devices, con-
pn junction diode was fabricated with Mg-doped CuCrO2 (p-type) verting light into electricity, where the pn junction photoactive
and ZnO (n-type) films, using PLD-grown AZO electrodes fabri- layer is composed of organic semiconductors. The most inves-
cated at room temperature (Fig. 4b). A rectification ratio of ~50 tigated OPV architecture has a bottom TCO electrode, a bulk-
from 2 to 2V was reported80. heterojunction blend of donor (p-type) and acceptor (n-type)
MO diodes for gas sensors using various pn junction architec- organic semiconductors, charge extracting layers and a top metal
tures have been investigated, including semiconductor blends81,82, electrode (Fig. 4e). Depending on the semiconductor/electrode
and coreshell83,84, bilayer or multilayer structures85,86. However, such interface arrangement, the transparent electrode collects holes and
sensors typically require >200C operating temperatures to reach the the metal electrode electrons (conventional architecture) or vice
molecular adsorption and desorption rates required for high respon- versa (inverted architecture). MOs are typically employed as the
sivity. Recently, resonant tunnelling devices using Cu2OSnO2 pn TCO electrode or as charge-extracting interfacial layers (IFLs) to
multilayer heterostructures were reported to exhibit excellent sensitiv- enhance PCE. The electron concentration (N) and carrier mobility
ity to H2S vapours at 25C (ref.87). Some studies have also proposed affect TCO electrical and optical properties, with N affecting both
all-MO diodes for photovoltaic cells. Here, Al-doped ZnO(n-type) the short wavelength transmittance cut-off limit (band gap) and
Ga2O3(i)Cu2O(p-type) thin-film heterojunction solar cells fabri- the long wavelength transmittance cut-off (plasma wavelength)98.
cated at 25C by PLD gave power conversion efficiencies (PCEs) of Typically, these optical limitations shift to shorter wavelengths with
5.38%, higher than optimized Cu2O solar cells88. Recently, nanosized increasing N, and for solar applications, high carrier mobility and
ZnO(n)Cu2O(p) and ZnO(n)TiO2(i)Cu2O(p) heterostructure low-N TCOs are preferred. As an exception to this rule, electronic
diodes were fabricated from vapour-phase-synthesized Cu2O nano structure engineering rather than doping has been recently used to
wires89, and a PCE of 0.39% was measured, suggesting the possibility suppress interband transitions in thermal epitaxy-grown SrVO3 and
of practical nanostructured oxide heterojunction solar cells. CaVO3 films, yielding high conductivity and transparency 99 even in
the presence of high carrier concentrations (N>2.21022cm3).
Memories Strong electronelectron interactions in these correlated materials
Random access memories (RAMs) are important data-storage com- lead to low screened plasma energies (<1.33eV) and good combined
ponents in logic circuits, and MOs are well-suited for resistive RAMs conductivity and transparency performance.

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NATURE MATERIALS DOI: 10.1038/NMAT4599 REVIEW ARTICLE
Wide bandgap MOs, for example, In2O3, SnO2 and ZnO, are use- e-IFLs on the ITO electrode119122, however, Cs2CO3 (ref.123) and
ful TCOs by keeping N < 1018 cm3 and adding secondary dopant TiO2 (ref.124) have also been reported. Again, nanoparticle-based
ions to increase the optical bandgap (Burstein-Moss effect). Thus, formulations allow process simplification, effectively eliminat-
the bandgaps of InAlO (ref.100) and ZnGaO (ref.101) (~3.8eV) ing high-temperature solgel annealing and enhancing the device
are higher than the parent In2O3 (~3.7eV) or ZnO (~3.2eV) host. lifetime125. Triple-junction OCSs with multiple photoactive lay-
However, ITO is by far the most used TCO electrode for organic ers have been recently fabricated using Li-doped ZnO interlayers
solar cells (OSCs) considering the low sheet resistance (~10 sq.1), (spin-coated, annealed at 100 C), to achieve a PCE = 11.83%
excellent transparency (optical bandgap ~4.0 eV), minimal toxic- (ref. 126). Furthermore, ITOZnO electrodes have been com-
ity, good etchability and facile film formation on glass and plastic bined with various MO h-IFLs, such as thermally evaporated V2O5
substrates12. Good ITO conductivity minimizes resistive losses to and MoO3, and various organic active materials127. Besides solgel
the collecting electrodes, whereas the transparency increases light methods, ALD was used to grow interfacial MO layers for OSCs at
absorption in the photoactive layer. Resistive losses become sig- low temperatures128. Using ALD-grown ZnO as an e-IFL (36 nm,
nificant in OSCs, especially for large-area devices (>0.1 cm2), and at 80 C) yields P3HT:PCBM cells with PCE = 4.18% on flexible
simulations reveal that hole-collecting electrode conductivity con- PET substrates129. Thermally evaporated PbO has also been used
tributes significantly to these losses102. It has been shown that OSC as an e-IFL for inverted devices, lowering the ITO work function
PCEs increase from 5.94 to 8.24%, when the hole-collecting ITO by ~1eV (ref.130). PbO-based P3HT:PCBM cells in combination
sheet resistance decreases from 40 to 5 sq.1 (ref. 103). Other with a MoO3 h-IFL at the metal hole-collecting electrode give PCEs
TCOs have been utilized in OSCs such as zinc indium tin oxide of ~4.00%. Regarding h-IFLs, amorphous V2O5 solutions processed
(ZITO; ~10sq.1)104 and InxCd1xOITO bilayers (~5.5sq.1)105. at ~100 C (ref. 131) and CuOx solgels have also been used in
Usually, polycrystalline TCO films on plastic suffer from significant inverted P3HT:PCBM cells132. Similar to p-type NiO, CuOx has a
performance degradation and cracking on tension and compressive CBM at ~5.3eV, matching the P3HT highest occupied molecular
mechanical stress. However, it was recently shown that PLD-grown orbital for hole extraction. Such cells have a PCE of ~4.02% with
a-ZITO on AryLite plastic is an excellent OPV electrode, with a sheet stability >1,000h.
resistance of ~20sq.1 and superior mechanical stability on mul- It should be mentioned that metal nanowire meshes typically
tiple bends about a 5mm radius106. Flexible AryLitea-ZITO-based silver nanowire (AgNW) networks have emerged as promising
PTB7:PC71BM cells provide PCE=6.42%. electrodes for OSCs. However, due to the large injection barrier
MO films have also been extensively used as IFLs for hole (h-IFL) between AgNWs and organic semiconductors, the OSCs suffer low
or electron (e-IFL) selective extraction from OSC active layers, both performance. Therefore, MO h-IFLs and/or e-IFLs are also used to
in conventional and inverted device architectures (Fig.4f). In con- replace PEDOT:PSS and/or LiF, respectively. Inverted P3HT:PCBM
ventional architectures, MO h-IFLs are primarily used to replace cells with a AgNW-based electron-collecting electrode utilized
the corrosive hole conductor PEDOT:PSS on ITO. In 2008, the first spin-coated TiOx and evaporated MoOx as the e-IFL and h-IFL,
use of PLD-grown NiO as a p-type h-IFL in P3HT:PCBM cells was respectively, affording a PCE of 3.1% versus 2.0% for PEDOT:PSS
reported, yielding an optimized PCE of 5.16% for a 10-nm-thick NiO h-IFL devices133. Recently, fully printed tandem OSCs on PET plas-
IFL versus 2.87% for the control107. In 2010, solution-processed NiO tic substrates using AgNW-based electron-collecting electrodes and
was deposited by spin-coating a Ni-based ink on ITO and annealing ZnO e-IFLs achieved an optimized PCE of 4.85% (ref.134). These
at 250C, affording P3HT:PCBM cells with PCE=3.6% compa- results demonstrate the potential of combining these two types of
rable to PEDOT:PSS cells108. Recently, PLD-grown NiO films were materials to engineer transparent electrodes.
studied as a function of processing parameters, such as atmospheric
gas ratio and growth temperature as well as post-deposition Ar and Outlook
O2 plasma treatment, to assess effects on film electronic structure Great progress has been made in understanding and implement-
and OPV performance109. Interestingly, substantial NiO work- ing new metal oxide optoelectronic materials, including crys-
function changes of ~1 eV occur on O2 plasma treatment. Other talline and amorphous transparent conductors (TCOs) and
MOs commonly used to replace PEDOT:PSS as an h-IFL are vapour- semiconductors. These materials now rival and complement other
deposited V2O5 (ref.110), MoO3 and WO3 (refs111,112). The Fermi unconventional semiconductors such as organics, CNTs and 2D
levels of these materials are very near the CBM and technically are materials. Capitalizing on unique MO properties, numerous elec-
n-type semiconductors113, yet they may function as p-type dopants tronic and optical devices have been demonstrated, with many
for the photoactive blend donor material (for instance P3HT) con- notable advances in the past several years. These include the follow-
sidering that their CBM lies below the donor highest occupied ing: (i) Advances in p-type semiconductors, opening possibilities
molecular orbital energy 114. MoO3 films prepared by spin-coating for p-type TFTs, pn junctions and oxide CMOS. Considering that,
nanoparticle suspensions exhibit properties similar to vapour- in contrast to organics and CNTs, MO transport has been largely
deposited films115,116. Solgel deposited V2O5 films spin-coated and limited to electrons, this advance significantly changes our under-
then annealed at low temperatures110 yield OSCs with performance standing of how MOs can be tuned for new functions. Nevertheless,
comparable to PEDOT:PSS cells but with improved durability. additional fundamental studies are needed to bridge the perfor-
The most common electron-extracting MO e-IFLs in con- mance gap between n- and p-type MO semiconductors. (ii) The
ventional OSC architectures typically replace LiF in contact with demonstration of unique charge-transport properties of AOSs ver-
the electron-collecting electrode, and are n-type TiO2 and ZnO. sus a-Si:H and a-chalcogenides, which enable performance not pos-
Furthermore, amorphous TiO2 films have been fabricated by spin- sible in a-chalcogenide materials. (iii) Low-temperature film growth
coating solgels directly on the OSC photoactive layer at tempera- on diverse substrates, including plastics, by a variety of techniques.
tures compatible with the organic materials117. ZnO has a higher e This has enabled the realization of high performance, flexible, and
than TiO2, mitigating recombination losses. Although solgels have transparent TFTs, with IGZO currently commercialized for OLED
been used for ZnO IFLs, spin-coatable nanoparticle formulations and next-generation liquid-crystal display backplane drivers. An
are more broadly used118. interesting question is whether less complex MOs can achieve
For inverted OSC architectures, MOs can be used to switch the IGZO performance and stability, with broader process windows.
ITO function from hole- to electron-collecting, thereby extracting (iv) Advances in solution-based MO deposition via numerous new
electrons and accommodating high work-function and stable top- techniques, including those using MO nanoparticles and nano
electrode metals. Typical inverted OPVs use solgel-derived ZnO wires. Various direct solution-phase MO film growth techniques

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REVIEW ARTICLE NATURE MATERIALS DOI: 10.1038/NMAT4599
have been developed, including solgel, spray pyrolysis, chemical 24. Lin, Y.-Y., Hsu, C.-C., Tseng, M.-H., Shyue, J.-J. & Tsai, F.-Y. Stable and high-
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