Materials Research of Perovskite Thin Films for Uncooled 

Infrared (IR) Detectors

by Wendy L. Sarney, Kimberley A. Olver, John W. Little, 

Frank E. Livingston, Krisztian Niesz, and Daniel E. Morse

ARL-TR-5600 July 2011

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Army Research Laboratory

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ARL-TR-5600 July 2011

Materials Research of Perovskite Thin Films for Uncooled 

Infrared (IR) Detectors

Wendy L. Sarney, Kimberley A. Olver, and John W. Little, 

Sensors and Electron Devices Directorate, ARL

Frank E. Livingston

The Aerospace Corporation

Krisztian Niesz and Daniel E. Morse

Institute for Collaborative Biotechnologies

University of California Santa Barbara

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Materials Research of Perovskite Thin Films for Uncooled Infrared (IR) 

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14. ABSTRACT

This report describes the highlights and summary of the year two, quarters two and three progress for the 6.2 project 

“Improved Sensitivity Low-Cost Uncooled IR Detector Focal-Plane Arrays.” This work occurred during the August 2009–

January 2010 time period. The program goals for year 2-quarters 2&3 corresponded to the continued expansion of our BaTiO3

nanomaterial synthesis capabilities and deposition methods, laser-induced pyroelectric phase conversion studies and nanoscale 

characterization of the pyroelectric activation process, and fabrication of IR test heterostructures for pyroelectrical analysis, 

along with the development of a technique for generating the requisite IR absorbing layer. 

15. SUBJECT TERMS

Laser processing, perovskites, uncooled infrared

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Wendy L. Sarney

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iii

Contents

List of Figures iv

List of Tables v

Acknowledgments vi

1. Introduction 1

2. Progress by The Aerospace Corporation (Aerospace) 2

2.1 Influence of Perovskite Film Thickness on Optical Band Gap Energy ..........................2

2.2 Enhancements to the Laser-scripted Pulse Modulation Setup ........................................5

2.3 Digitally-scripted Laser Genotype Direct-write Processing – Continued Success!........7

3. Progress by the Institute for Collaborative Biotechnologies (ICB) 12

3.1 Tc with Ba1-xSrxTiO3; Doping with CeO2; Preparation of Thicker Films.....................12

3.2 Further Progress in Scale-Up and Delivery to Quallion................................................16

4. Progress by the Army Research Laboratory (ARL) 17

4.1 Sacrificial Layer Deposition; Electrical Characterization; Nanostructured IR 

Absorbing Layer Development ..............................................................................................17

4.1.1 Sacrificial Layer Deposition..............................................................................17

4.1.2 Electrical Characterization ................................................................................18

4.1.3 Nanostructured IR Absorbing Layer Development...........................................18

4.2 Update of Proposed Processing Steps...........................................................................19

5. Plans and Goals for Year 2 Quarter 4 20

6 Metrics for Year 2 Quarters 2 and 3 21

6.1 Publications...................................................................................................................21

6.2 Conferences and Symposia ...........................................................................................21

7. References 23

List of Symbols, Abbreviations, and Acronyms 24

Distribution List 25
iv

List of Figures

Figure 1. Project schedule for year 2. .............................................................................................1

Figure 2. (a) Optical transmission spectra measured for BaTiO3 films with varying thickness. 

(b) First-derivative plots of the transmission spectra that were used to determine that band 

gap energies (Eg) as a function of film thickness.......................................................................3

Figure 3. Compilation of band gap energies for BaTiO3 as a function of film thickness, 

where Eg values have been derived from literature sources (red) and compared with the 

Eg values measured for the ICB films (blue). The solid lines represent linear fits to the 

data, and are intended as a visual aid. The corresponding energies of the laser processing 

wavelengths (= 266 nm and =355 nm) are also shown (grey) for comparison. ...................4

Figure 4. Photographic images of the laser genotype pulse modulation optical beam lines 

(left) and the new dual-beam SHG spectroscopic detection system (right) for phase 

conversion analysis during static exposures and dynamic raster patterning..............................6

Figure 5. Raman spectra measured for BaTiO3 thin-films following conventional laser 

direct-write processing at =266 nm and 5 kHz........................................................................8

Figure 6. SEM images of BaTiO3 thin-films that were acquired (a) prior to laser exposure 

and (b)–(d) following conventional laser direct-write processing at =266 nm. ......................9

Figure 7. Raman spectra measured for BaTiO3 thin-films following digitally-scripted laser 

genotype direct-write processing at =266 nm and 5 kHz. The laser pulse scripts 

corresponded to the following parameters: script 1, 90 pulses, 1.5 J·cm–2; script 2, 180 

pulses, 1.6 J·cm–2; script 3, 240 pulses, 3.1 J·cm–2(max).......................................................11

Figure 8. AFM images of BaTiO3 thin-films that were acquired (a) prior to laser exposure 

and (b) following digitally-scripted laser genotype direct-write processing and 

pyroelectric phase conversion at 355 nm. Note that the perovskite film remains 

unperturbed during the laser-induced phase transformation process when laser pulse 

“scripting” is employed for high fidelity heat control. ...........................................................12

Figure 9. TEM and XRD analyses of BSTO nanoparticles prepared by vapor diffusion 

catalytic synthesis. Dotted lines on the XRD curve show the positions of the (110) 

reflections in pure bulk BaTiO3 and SrTiO3, respectively.......................................................13

Figure 10. PTCR (positive thermal coefficient of resistivity) of the sintered BSTO ceramic, 

showing a reduced Curie temperature of ca. 80 °C. ................................................................14

Figure 11. TEM image of CeO2 nanoparticles prepared by vapor diffusion catalytic 

synthesis...................................................................................................................................14

Figure 12. SEM images of the high-quality doped BSTO films produced by layer-by-layer 

deposition followed by annealing. ...........................................................................................15

Figure 13. IR test heterostructure..................................................................................................17

Figure 14. Wire bonding for capacitance measurements..............................................................18

Figure 15. Processing steps required for the generation of nanostructured Si pillars for 

enhanced IR absorption............................................................................................................19
v

Figure 16. AFM images of Au particle formation prior to etching. .............................................19

Figure 17. Pixel formation accomplished via conventional approaches......................................20

Figure 18. Pixel formation accomplished via laser-induced pyroelectric activation...................20

List of Tables

Table 1. Operational characteristics of the laser system integrated into the laser genotype 

direct-write processing setup. ....................................................................................................6
vi

Acknowledgments

We acknowledge support by the Institute for Collaborative Biotechnologies through grant 

DAAD19-03-D-0004 from the U.S. Army Research Office and The Aerospace Corporation 

Independent Research and Development (IR&D) Program and the Product and Development 

(PDP) Program.
1

1. Introduction

This report describes the highlights and summary of the year two, quarters two and three

(Y2Q2/3) progress for the 6.2 project “Improved Sensitivity Low-Cost Uncooled IR Detector 

Focal-Plane Arrays.” This work occurred during the August 2009–January 2010 time period. The 

project schedule for year 2 is summarized in figure 1. A description of the background technical 

information and earlier progress is discussed in prior technical reports (1–4).

Figure 1. Project schedule for year 2.

The program goals for year 2-quarters 2&3 corresponded to the continued expansion of our 

BaTiO3 nanomaterial synthesis capabilities and deposition methods, laser-induced pyroelectric 

phase conversion studies and nanoscale characterization of the pyroelectric activation process, 

and fabrication of IR test heterostructures for pyroelectrical analysis, along with the development 

of a technique for generating the requisite IR absorbing layer. Respective team highlights 

include: 
2

Aerospace: Investigated the optical transmission properties of functionalized BaTiO3 

nanoparticle films as a function of film thickness, which will help to optimize the laser-induced 

pyroelectric phase conversion process. We continued investigations into the laser-induced 

pyroelectric cubic-tetragonal phase conversion of functionalized BaTiO3 nanoparticle thin-films 

at multiple UV wavelengths – including laser-scripted modulation at =355 nm and intensity 

modulation and variable exposure at =266 nm. Efforts also focused on the development and 

implementation of piezoresponse force microscopy (PFM) techniques for nanoscale 

characterization of the laser-induced pyroelectric phase activation. We further expanded the 

capabilities and versatility of the laser-scripted processing and spectroscopic detection schemes 

to include a broader range of processing wavelengths, pulse durations, and pulse repetition rates. 

ICB: Extended the bio-inspired vapor diffusion catalytic synthesis methods to include the growth 

and deposition of functionalized, high purity barium strontium titanate (Ba1–xSrxTiO3, BSTO) 

nanoparticle thin-films, where the Ba/Sr composition can be altered to precisely tune the electric 

properties of the ceramic films. Doping of the BSTO nanoparticles with CeO2 has also been 

accomplished, which will enhance UV absorption in the native films and improve the laserinduced phase conversion efficiency. Further progress regarding scale-up and sonicationaccelerated synthesis was achieved, along with the improved methods for the deposition of thick 

micrometer-scale BSTO. 

ARL: Investigated the implementation of potential release (sacrificial) layers for the formation of 

the requisite suspended perovskite MEMS membranes, including polymethyl methacrylate 

(PMMA) and other standard photoresists. Continued and expanded the development of the IR 

test heterostructure, which included electrical characterization, fabrication of nanostructured Si 

layers for enhanced IR absorption, and improvements in the proposed detector pixel processing 

protocol. 

All project teams have accomplished their respective planned milestones for Y2Q2/3 with 

distinction, and highlights of the major activities are provided in the subsequent sections of this 

report. 

2. Progress by The Aerospace Corporation (Aerospace) 

2.1 Influence of Perovskite Film Thickness on Optical Band Gap Energy

Our second and third quarter efforts for year 2 have focused on the influence of film thickness 

and morphology on the inherent band gap energies of the BaTiO3 nanostructured films, which 

will affect the laser-material coupling efficiency as well as the extent of pyroelectric phase 

conversion. Figure 2a shows the optical transmission spectra that were measured for BaTiO3

films as a function of film thickness, where the film thickness ranged from ca. 200 nm to 5 m 

and the optical spectra have been corrected for reflection and scattering and thus represent the 
3

pure transmission characteristics of the nascent film. The BaTiO3 nanoparticles were deposited 

on 1 mm thick optical quality quartz substrates at room temperature and ambient pressure. For 

films with a thickness <500 nm, the BaTiO3 nanoparticles were pre-functionalized with oleic 

acid and dispersed in a hexane colloidal solution for eventual layer-by-layer spin coating. For 

films with a thickness >500 nm, the BaTiO3 films were cast as nanoparticle suspensions in 

methanol/butanol, and then dried in a vacuum desiccator for 48 hr. 

Figure 2. (a) Optical transmission spectra measured for BaTiO3 films with varying thickness. (b) First-derivative 

plots of the transmission spectra that were used to determine that band gap energies (Eg) as a function of 

film thickness. 

The spectra shown in figure 2a reveal high transparency in the visible and near-IR regions 

particularly for the BaTiO3 films with thicknesses <1 m – and suggest only a small degree of 

local surface roughness and good film homogeneity. The thinner films display higher 

transparency and retain higher homogeneity and less roughness; these characteristics have been 

confirmed with complementary analysis using contact profilometry, scanning electron 

microscope (SEM) and atomic force microscopy (AFM) techniques. For the thicker micron-sized 

films (>1 m), inter-band transitions occur at wavelengths of λ<450–500 nm, and the 

transmission falls rapidly to less than 10% at wavelengths of λ<400 nm. In contrast, inter-band 

transitions occur at wavelengths of λ<300 nm for the thinner 200–500 nm-thick films, and the 

10% cut-off occurs at UV wavelengths of <260 nm.

Figure 2b displays the corresponding first-derivative plots of the optical transmission spectra as a 

function of BaTiO3 film thickness. The band gap energies were estimated from the peak maxima 

positions, and the results presented in figure 2b reveal that the band gap energies for BaTiO3

exhibit a strong dependence on film thickness. The calculated band gap energies displayed the 

following trend with film thicknesses denoted in parentheses: E=3.27±0.4 eV (3–5 m), 

3.84±0.2 eV (0.5–1 m), 3.95±0.1 eV (300–500 nm), and 4.12±0.05 eV (200–300 nm). Our 

results also reveal that the fluctuations in the band gap energies that were observed previously 
4

with thicker and unfunctionalized BaTiO3 nanoparticle films have been notably reduced, and 

laser light scattering has been decreased as well.

While the band gap energy fluctuations have been reduced, the absolute band gap energies for 

the thinner and functionalized BaTiO3 films are appreciably blue-shifted compared with the

thicker micrometer-scale films. Figure 3 summarizes the band gap energies as a function of 

BaTiO3 film thickness, where the band gap values have been derived from a survey of the 

relevant literature and from the composite ICB sample sets. The literature data encompass a 

diverse array of BaTiO3 synthesis and deposition methods, including melt-grown single crystals

(5), pulsed laser deposition (PLD) (6), sol-gel (7–9), spray pyrolysis (10), and molecular beam 

epitaxy (MBE) (11). Clearly, the band gap energies can be influenced by factors other than film 

thickness – such as synthesis and deposition method, extent of crystallinity and crystallite grain 

size, and intrinsic and extrinsic stresses (defects, lattice mismatch). However, when applying a 

specific protocol for particle synthesis and thin-film preparation, the band gap energies are 

highly consistent and appear to correlate quite well with the BaTiO3 film thickness. 

Figure 3. Compilation of band gap energies for BaTiO3 as a function of film thickness, 

where Eg values have been derived from literature sources (red) and compared 

with the Eg values measured for the ICB films (blue). The solid lines represent 

linear fits to the data, and are intended as a visual aid. The corresponding energies 

of the laser processing wavelengths (= 266 nm and =355 nm) are also shown 

(grey) for comparison.
5

This film-thickness dependent behavior of the band gap energy will severely impact the selection 

of the appropriate laser processing wavelengths and other laser parameters that are requisites for 

effective laser energy coupling and optimal pyroelectric phase transformation. The extent to 

which the band gap energy determines the laser-material coupling and phase state selection 

efficiency is related to the mechanisms and energy dependence of the laser-induced phase 

conversion process; we are currently exploring the photon dependence of the pyroelectric cubicto-tetragonal phase conversion in BaTiO3 thin-films at multiple UV laser wavelengths in order to 

optimize pyroelectric activation. 

Laser processing at =355 nm permits phase control in thick micrometer-scale BaTiO3 films due 

to the enhanced optical penetration depth, but requires higher incident laser energies for phase 

conversion due to the reduced absorption. The photon flux at =355 nm must be carefully 

modulated to preclude damage to the underlying adhesion and electrical contact layers. 

Conversely, laser processing at =266 nm facilitates access to a much wider range of film 

thicknesses with enhanced energy absorption, smaller optical penetration depth, and thus higher 

localized energy density. However, this increase in energy absorption leads to a smaller laser 

processing window and requires exquisite laser pulse script control and per-pulse intensity 

modulation. 

2.2 Enhancements to the Laser-scripted Pulse Modulation Setup

The optical results presented in figures 2 and 3 strongly support the notion that the laser 

processing method must be highly versatile and adaptable, and facilitate phase conversion over a 

wide range of laser wavelengths, pulse durations and repetition rates. Figure 4 displays 

photographic images of the various optical beam lines that comprise the laser-scripted genotype 

pulse modulation system (left panel) and spectroscopic pump-probe detection scheme (right 

panel). The laser genotype processing setup now retains four separate optical beam lines, where 

each beam lines includes the appropriate polarizers, waveplates, focusing and collimation lenses, 

and electro-optic Pockels cell modulators and amplifier assemblies that are required for positionsynchronized and laser-scripted direct-write processing. The revised laser pulse modulation setup 

also includes four laser systems that span a broad range of laser processing parameters and 

capabilities. With adaptations to our current laser systems and optical configurations, we can 

examine laser phase conversion under a wide range of wavelengths (250–1100 nm), along with 

variations in pulse length (100 fs–5 ns) and pulse repetition rate conditions (5 kHz–80 MHz). 

The specifications for the integrated laser systems are comprehensively summarized in table 1. 
6

Figure 4. Photographic images of the laser genotype pulse modulation optical beam lines (left) and the new dualbeam SHG spectroscopic detection system (right) for phase conversion analysis during static exposures 

and dynamic raster patterning. 

Table 1. Operational characteristics of the laser system integrated into the laser genotype direct-write processing 

setup.

Laser system Operational parameters

wavelength rep. rate pulse width power

diode-pumped, mode-locked Ti:sapphire 

(Spectra-Physics, MaiTai)

750–920 nm 80 MHz 100 fs 1 W

diode-pumped, Q-switched intra-cavity 

doubled Nd:YLF 

(Spectra-Physics Evolution-30) 

527 nm 5 kHz 300 ns 30 W

Ti:sapphire regenerative amplifier with 

pulse stretcher/compressor (SpectraPhysics Spitfre) 

750–920 nm 5 kHz 100–500 fs 2.5 W

diode-pumped, mode-locked Nd:YVO4 

laser with SESAM 

(Spectra-Physics Vanguard) 

1064 nm 

355/532 nm 

80 MHz 2 ps 4 W

1 W

diode-pumped, mode-locked Nd:YVO4 

(Spectra-Physics BL6 series) 

1064 nm 10–50 kHz 6 ns 4–7 W

Our recent efforts in year 2 have also focused on the continued development and implementation 

of a spectroscopic detection scheme for end-point analysis of the laser-induced pyroelectric 

activation and phase conversion process, where we have now constructed and tested the dualbeam second harmonic generation (SHG) and photoemission setup. The dual-beam SHG 

spectroscopic detection scheme permits the simultaneous delivery of the UV laser processing 

beam and IR SHG pump-beam to a substrate under dynamic patterning conditions and static 

exposure conditions; these modifications will help facilitate laser pulse script optimization and 

refinement via SHG and photoluminescence measurements, along with improving process and 

quality control. The IR probe beam is fiber-coupled to the substrate surface and also feeds into 

the static exposure beam line.
7

2.3 Digitally-scripted Laser Genotype Direct-write Processing – Continued Success! 

We have continued to investigate the capability of using multi-wavelength laser-scripted directwrite processing techniques to induce site-selective and patterned micro- and nano-scale 

transformation of BaTiO3 nanoparticle aggregates from the nascent pyrolectrically-inactive cubic 

phase to the pyroelectrically-active tetragonal phase. Recall that our intent is to use laser 

irradiation to achieve in-band excitation of the BaTiO3 crystal, where the resonant irradiation 

energy is above or very close to the band gap of BaTiO3, and will lead to the excitation of 

valence electrons and the formation of excited electronic states. The exchange of energy between 

the electronic excited states and lattice vibrational energy will lead to a rapid temperature rise in 

the crystal lattice (i.e., electron-lattice coupling) and a concomitant cubic-to-tetragonal phase 

transition. 

Our recent research efforts have focused on the implementation of deep-UV laser processing at 

=266 nm for pyroelectric phase activation. Like our prior experimental investigations using 

=355 nm irradiation, two distinct laser processing approaches were employed to examine lasermediated pyroelectric phase conversion in the bio-inspired BaTiO3 thin-films at =266 nm: 

conventional laser direct-write processing and genotype-inspired, digitally-scripted laser 

processing. Again, the contrasting results from these two approaches clearly illustrate the 

importance of synchronized, high fidelity photon modulation during laser patterning for optimal 

phase conversion. In the conventional laser direct-write processing scenario, the incident and 

repetitive laser pulse train remains un-articulated, and the only modulation employed 

corresponds to simple power control, i.e., the laser pulse intensities are uniformly attenuated to 

achieve the desired static power level and per-pulse fluence for material exposure and 

processing. 

Figure 5 provides a compilation of the Raman spectra that were measured for a set of 200–300 

nm-thick BaTiO3 thin-films following conventional laser direct-write processing at =266 nm. 

The vertical lines denote the locations of the prominent Raman-active bands associated with the 

tetragonal phase of BaTiO3, which occur at 305 cm–1, 540 cm–1, and 720 cm–1. The cubic-totetragonal phase conversion was examined over a wide laser parameter space, including power 

and per pulse intensity (conversion threshold), pulse repetition rate (thermal diffusion and heat 

capacity), pulse length (conversion kinetics), and total exposure dose (sequential phase 

conversion). The variation in laser pulse repetition rate will help to illuminate the kinetics of 

energy transfer into the BaTiO3 crystal lattice system. Additionally, the variation in pulse length 

will assist in determining whether partial or complete phase conversion can be accomplished 

during a single pulse event (intra-pulse) or by the administration of a succession of laser pulses 

(inter-pulse).
8

Figure 5. Raman spectra measured for BaTiO3 thin-films following conventional laser direct-write 

processing at =266 nm and 5 kHz.

Despite the increased absorption at =266 nm – where the absorptivity of the ultra thin BaTiO3

films is ca. 60% compared to only ca. 10% at =355 nm – appreciable phase transformation was 

not detected, but instead was accompanied by significant film disruption and desorption. For 

these conventional laser processing experiments, the average number of pulses delivered to each 

laser spot ranged from 30 to 300 pulses, the repetition rates were varied from 10 kHz to 50 kHz, 

and the per-pulse fluence ranged from 0.64 J·cm–2to 3.04 J·cm–2. The lower power and higher 

pulse repetition rate exposures yielded little change in the Raman spectra, and indicate that the 

pulse energies and related thermal transients were insufficient to induce phase conversion. The 

higher power and lower pulse repetition rate exposures also show no evidence of structural phase 

conversion, but did reveal appreciable film fracture and material desorption due to excessive heat 

loading and thermal confinement. 

Figure 6 shows the surface topography of the BaTiO3 thin-films following conventional laser 

direct-write processing at =266 nm. A SEM image of the as-received unexposed cubic BaTiO3

thin-films is displayed in figure 6a and reveals that the native BaTiO3 thin-films are relatively 

smooth and crack-free, highly crystalline and compositionally homogeneous. However, in the 

absence of laser genotype pulse “scripting” and position-synchronized photon delivery, lasermaterial energy coupling is inefficient under conventional laser direct-write irradiation at =266 

nm, and the phase conversion is sporadic and results in detrimental material processing effects –
9

including laser light scattering, variation in absorbed energy, enhanced energy confinement, nonuniform heating and residual stress and fracture.

Figure 6. SEM images of BaTiO3 thin-films that were acquired (a) prior to laser exposure and (b)–(d) following 

conventional laser direct-write processing at =266 nm.

Figure 6b shows a SEM image of the BaTiO3 thin-film surface following laser patterning at =266 

nm, where the average number of laser pulses administered to each spot was 30, the pulse 

repetition rate was 10 kHz, and the per-pulse fluence was set to 6.0 J·cm–2. The SEM results 

reveal a rough and highly corrugated surface morphology associated with significant material 

desorption and particulate ejection. Higher repetition rate and lower per-pulse fluence exposures 

were also employed, but caused similar damage to the BaTiO3 thin-films. Figures 6c and 6d 

display the SEM images acquired following 30 kHz laser irradiation at =266 nm, where the 

average number of laser pulses delivered to each spot has been increased to 90 with per-pulse 

fluences of 1.5 J·cm–2and 2.7 J·cm–2, respectively. The SEM results again indicate marked 

surface disruption, which was manifested in particle sintering and aggregation, along with 

substantial film cracking and delamination. 

The composite results shown in figures 4 and 5 strongly suggest that high fidelity laser pulse 

modulation and enhanced heating control are needed to promote pyroelectric phase conversion, 

while maintaining the overall integrity and mechanical stability of the BaTiO3 thin-films. Figure 
10

6 displays a set of Raman spectra that were acquired following laser processing of 300-nm-thick 

BaTiO3 thin-films using genotype-inspired, digitally-scripted laser direct-write techniques. The 

Raman results shown in figure 6 correspond to BaTiO3 thin-films that were exposed to incident 

laser irradiation at =266 nm (5 kHz; 520 fs pulse width) using the composite laser pulse scripts 

shown in the insets. The composite laser pulse scripts were synchronously delivered to each 

laser-irradiated spot during patterning, where the laser raster pattern corresponded to a 2 mm x 

2 mm square with a sequential line fill, and a step-over between line scans that was equivalent to 

the laser spot size. The laser pulse scripts comprised high intensity, ultra short pulses at a low 

repetition rate with the following parameters: Script 1, 90 pulses, 1.5 J·cm–2; Script 2, 180 

pulses, 1.6 J·cm–2; Script 3, 240 pulses, 3.1 J·cm–2(max). The laser-scripted processing results 

reveal that the pyroelectric phase transformation can be accomplished by the administration of a 

succession of laser pulses, i.e., inter-pulse conversion – where each pulse partially converts 

nano- and microscale domains of the BaTiO3 thin-film from the cubic phase to the tetragonal 

phase. Metered laser exposure doses can, therefore, be used to induce sequential phase 

transformation, which will facilitate fine phase state control and laser-tuning of the electrical and 

pyroelectric properties of the BaTiO3 thin-films. The enhanced conversion observed with pulse 

script 3 (which contained an initial “ramp” pulse profile) indicates that the laser pulse scripts 

must account for dynamic changes in the film’s properties, such as the refractive index, heat 

capacity and optical defect density; we are currently exploring these effects and their impact on 

the extent of laser-induced phase transformation.

The importance of laser pulse “scripting” and appropriately tailoring the photon flux to control 

heat flow in the BaTiO3 crystal lattice is highlighted in figure 7, which compares the nanoscale 

surface topography before and after laser genotype processing at =355 nm (80 MHz, 10 ps 

fwhm). Figure 8a displays an AFM image acquired prior to laser exposure (as-received), and 

corresponds to a relatively smooth BaTiO3 thin-film with a nominal rms surface roughness of 

~156 nm. Following laser-scripted exposure at =355 nm (~1x106pulses, per-pulse fluence=

3.6 mJ·cm–2), the AFM results reveal that the BaTiO3 thin-film remains undisturbed with a 

comparable rms surface roughness of ~140 nm and no measurable material desorption of 

particulate ejection. This is in marked contrast to the substantial damage to the BaTiO3 thin-film that 

was observed using conventional laser direct-write processing techniques (cf., figure 6).
11

Figure 7. Raman spectra measured for BaTiO3 thin-films following digitally-scripted laser genotype 

direct-write processing at =266 nm and 5 kHz. The laser pulse scripts corresponded to the 

following parameters: script 1, 90 pulses, 1.5 J·cm–2; script 2, 180 pulses, 1.6 J·cm–2; script 3, 

240 pulses, 3.1 J·cm–2(max).
12

Figure 8. AFM images of BaTiO3 thin-films that were acquired (a) prior to laser exposure and 

(b) following digitally-scripted laser genotype direct-write processing and pyroelectric 

phase conversion at 355 nm. Note that the perovskite film remains unperturbed during 

the laser-induced phase transformation process when laser pulse “scripting” is employed for 

high fidelity heat control.

3. Progress by the Institute for Collaborative Biotechnologies (ICB)

3.1 Tc with Ba1-xSrxTiO3; Doping with CeO2; Preparation of Thicker Films

ICB prepared and provided our Aerospace and ARL partners films composed of oleic acid 

functionalized Ba1-xSr x TiO3 (BSTO) and CeO2-doped BSTO nanoparticles synthesized by vapor 

diffusion catalysis from Ba/Ti- and Sr/Ti bimetallic alkoxide precursors with or without addition 

of a cerium alkoxide precursor (figures 9, 11, and 12). We found that this method enables us to 

precisely tune the electric properties of the final ceramics (e.g., the phase transition temperature) 

through carefully adjusting the Ba:Sr ratio by appropriate control of the mixture of the precursor 

materials. Electrical characterization after annealing showed that the nanopowder consisting of 

15% Sr and 85% Ba (metal content was determined by ICP) exhibits a significant decrease in the 

Curie temperature (Tc) from the 120 °C, characteristic of bulk BaTiO3, to ~80 °C (figure 10). 

We and our partners, therefore, chose BSTO as a model system for further investigation because 

it has several desirable properties for both IR detector and laser processing applications. These 

include a relatively large dielectric constant, good pyroelectric response near room temperature, 

low dielectric loss and leakage current, and phase transition temperature controllable by the 

amount of Sr incorporated.
13

Figure 9. TEM and XRD analyses of BSTO nanoparticles prepared by vapor diffusion catalytic synthesis. 

Dotted lines on the XRD curve show the positions of the (110) reflections in pure bulk BaTiO3

and SrTiO3, respectively.
14

Figure 10. PTCR (positive thermal coefficient of resistivity) of the sintered 

BSTO ceramic, showing a reduced Curie temperature of ca. 80 °C. 

Figure 11. TEM image of CeO2 nanoparticles prepared by vapor diffusion catalytic synthesis. 
15

Figure 12. SEM images of the high-quality doped BSTO films produced by layer-by-layer deposition followed by 

annealing. 

To increase the throughput and efficiency of laser-induced phase transformation in the thin-films 

(~210 nm thick, with potentially fast response time), nanoparticulate CeO2 exhibiting high 

photon absorption in the UV range was incorporated into the nanopowder prior to film 

deposition. For this purpose, we used a method we recently reported for the synthesis of 3.5 nm 

ceria nanoparticles from alkoxide precursors under conditions similar to those used for BTO or 

BSTO nanoparticle synthesis (figure 11), thereby promoting the formation of the two oxide 

materials simultaneously.

To produce this composite film, the appropriate amounts of Ba/Ti- and Sr/Ti bimetallic alkoxides 

were mixed in the precursor solution (to yield Ba1–xSrxTiO3, x = 0.15) with the addition of 

cerium isopropoxide (Ce(OC3H7)4) prior to hydrolysis and polycondensation. The targeted CeO2

concentration in the resulting solid nanopowder was 0.03 wt%. After collection of the resulting 

nanoparticle composite, oleic acid was added in hexane followed by sonication to functionalize 

the surface of the nanoparticles. After precipitation and intensive washing, the solid powder was 

finally re-dissolved in non-polar solvents (e.g., hexane, toluene), in which it remained stable for 

days. The colloid nanocrystals were then subjected to layer-by layer deposition through spin 

coating to make thicker films for better pyroelectric response. Each deposition step was followed 

by a subsequent annealing cycle at 300 °C to remove hydrocarbons and to densify the films. 

Previous results showed that thick films (~5 m) cracked when heated to 300 °C as a result of 

the gas evolution during annealing. We successfully circumvented that problem in this case by 

depositing the doped BSTO in thinner layers, with heating and cooling cycles performed at very 

low ramping rates (2 °C/min) to avoid cracking. SEM characterization shows that the films not 

only survived the annealing steps, but there was a significant densification due to particle 

rearrangement and the removal of the residual organics (figure 12). Thickness of the first film 

thus changed from the initial value of 850 nm to 550 nm after annealing at 300 °C for 2 hr; each 

additional layer, after annealing, produced a further significant increase in film thickness without 

the introduction of cracks. Thus, the thickness after deposition of the 2nd layer was 1.10 m, and 

after deposition of the 3rd layer, 1.44 m.
16

3.2 Further Progress in Scale-Up and Delivery to Quallion

a. Routine production doubled again: Using the mid-scale reactor design shown in our 

previous reports, we now have increased routine production of 7 nm BaTiO3 and Ba1–xSrxTiO3

nanoparticles to 250 g/batch (a doubling from our previous routine production of 100g/batch). 

Characterization by XRD, XPS, and TEM shows the product to be the same high quality and 

purity crystalline material as previously reported, with quantitative yield. Results are reported in 

a manuscript submitted to Nature Protocols. 

b. Progress toward continuous production: Progress on the construction of a large-scale 

reactor is nearing completion. This will enable trials of continuous-flow production with 

automated controls. This reactor incorporates several changes in design to increase throughput, 

including the use of nebulizers to deliver the reactants as a fine mist of micro-droplets, thereby 

accelerating diffusion and the resulting reaction kinetics governing synthesis. Preliminary trials 

of the apparatus operated with manual control produced pure, highly crystalline nanoparticles of 

BaTiO3 with no contaminants detectable.

c. Increase in throughput with sonication-accelerated synthesis: Sonication is being 

optimized experimentally, in an effort parallel to that described above, to increase the speed 

throughput of synthesis. Results show considerable promise: 

We found that ultrasonication significantly accelerates the quantitative conversion of the 

bimetallic alkoxide precursor to the highly crystalline final perovskite (BaTiO3) in only 3 h, 

representing a significantly increased throughput compared to previous results using vapor 

diffusion catalysis alone (typically requiring 2 days for completion of the process. (The high 

quality, quantitative yield and purity of the product were confirmed by XRD, XPS, TEM, Raman 

spectroscopy, and DTA analyses.) 

Our experimental analyses allow us to conclude that major factors responsible for the 

dramatically increased crystallization rates observed in the sonication-assisted syntheses can be 

attributed to the enhanced transport of water/acid catalyst molecules into the metal alkoxide 

precursors, the increased mixing rate of the alkoxide and water molecules and the accelerated 

formation of nucleation centers on the cavitation bubbles. Agitation of the precursor solutions 

through high-intensity sonication facilitates the formation of high surface areas of the liquid 

precursors, enhancing contact with the acidic water mixture, the transport of which is greatly 

increased either through an increase in evaporation rate or the formation of micro-droplets by 

sonication. The enhanced diffusion rate of water and acid molecules results in faster mixing of 

the reaction components. Finally, the increased crystallization rate, a significant and well-known 

effect of sonication, also is likely to contribute to the accelerated synthesis of the oxide 

nanoparticles. It also is possible that, as a consequence of the collapse of high-energy cavitation 

bubbles, the evaporation rate of solvent from the precursor solution is increased as well, further 

contributing to the shortened diffusion path for the water molecules. Furthermore, we have 

observed a mist of micro-droplets generated from the precursor solution above the liquid level, 
17

and solid product floating on the liquid surface within only half an hour after the start of 

sonication. This observation suggests the formation of small droplets with high surface area and 

high surface energy during the initial stages of product growth. These microscopic aerosol pools 

contain the reactive precursor, which can interact instantly with the aqueous catalyst through 

droplet collision, producing small oxide and perovskite nanoparticles. This mechanism is the 

subject of our ongoing investigation, focusing on the droplet size dependency, controlled by 

sonication in the MHz frequency regime, of the size of nanocrystals produced, and the possibility 

of making this process continuous. 

These results are reported in a manuscript now in press in Nano Today. 

Further improvements are now under investigation using tunable megahertz ultrasonication of 

both the precursor and catalyst.

4. Progress by the Army Research Laboratory (ARL) 

4.1 Sacrificial Layer Deposition; Electrical Characterization; Nanostructured IR 

Absorbing Layer Development

4.1.1 Sacrificial Layer Deposition 

In order to achieve low thermal mass, the proposed final structure includes a suspended MEMs 

membrane (figure 13). We must be able to release the BaTiO3 film from the substrate without 

damaging the film. 

Figure 13. IR test heterostructure. 

We began investigating potential release layers. We began by spin-coating PMMA, which is an 

inexpensive, transparent thermoplastic commonly used as photoresist in electron beam 

lithography. The next step was to evaporate Pt onto the PMMA layer (to serve as the bottom 

electrical contact). The Pt did not adhere to the PMMA.
18

We then attempted to use AZ-5214E, which is a photoresist intended for lift-off techniques. We 

were able to evaporate a well-adhering bottom metal electrode layer or BST layer deposition. 

Ultimately, AZ-5214E will not work in the final structure, since it cannot be exposed to 

temperatures above 120 °C. The current structure will serve as a practice tool for lifting off and 

handling the membrane and for studying its physical properties.

4.1.2 Electrical Characterization

The laser-activated tetragonal BaTiO3 pixels must be electrically isolated from one another. We 

wire bonded a structure, as shown in figure 14, for the purpose of capacitance measurements. 

After numerous attempts, we are finding that all structures that include the top metal layer are 

electrical shorts. By using epoxy to attach wires to a film that did not have a top metal contact, 

we found the film to be electrically resistive, as expected. XPS studies are in progress to 

determine if the top or bottom electrode layer is diffusing into the BaTiO3 film. Another potential 

source for electrical shorting would be metal traveling through micropores in the film, although 

earlier SEM did not indicate that this is likely.

Figure 14. Wire bonding for capacitance measurements. 

4.1.3 Nanostructured IR Absorbing Layer Development

Thermal detectors require a layer similar to a thin coating of black paint that absorbs a wide 

range of wavelengths and heats up. The heat is transferred to the BT layer and the pyroelectric 

voltage is generated. We are developing a low cost technique that is temperature-compatible with 

the bio-inspired BaTiO3 films and with ROIC technology.

We have grown a series of multilayer films comprising silicon/gold-nanoparticles and 

silicon/silicon dioxide/gold-nanoparticles to determine the required heat treatment (to form the 

nanoparticles) and etch parameters (to create the nanostructures in the surface of the film) 

required to make the film strongly absorbing in the 3 to 12 micron wavelength band. A 

schematic of the structure is shown in figure 15. The films are characterized using AFM, SEM 

and Fourier transform infrared spectroscopy. Figure 16 shows the particle formation after the 

heating but before the etch process.
19

Figure 15. Processing steps required for the generation of nanostructured Si pillars for enhanced IR absorption. 

Figure 16. AFM images of Au particle formation prior to etching. 

4.2 Update of Proposed Processing Steps 

After the second year review, it became clear that a comparison of our processing steps with 

conventional methods was needed. We updated our proposed processing steps to incorporate 

changes from our original proposal.

The standard optical lithography pixel delineation process includes: 

a. spinning a liquid photoresist onto the wafer 

b. baking the wafer for about an hour, exposing the wafer (the mask could have several arrays 

on it depending on the size)

c. developing the resist (minutes), rinse and dry, then any etching or deposition required 

d. for a complicated structure, a wafer will go through the photolithographic steps (a-c) 

several times (~50 times). 

Figure 17 shows a film grown by conventional MBE with pixels formed by photolithography, 

followed by substrate thinning, IR absorbing layer deposition, and flip-chip bonding to a fan-out 

or ROIC.

Figure 18 shows a similar process using laser-induced pyroelectric activation and bump bonding 

to a Si fan-out. This procedure will be used to prove proof-of-principal. These steps, made 

possible by low-temperature growth and site-specific laser processing, are not reliant on 

photolithography or flip-chip bonding, and there is no substrate thinning step.
20

Figure 17. Pixel formation accomplished via conventional 

approaches.

Figure 18. Pixel formation accomplished via laser-induced 

pyroelectric activation.

5. Plans and Goals for Year 2 Quarter 4

In the coming quarter, we will continue to expand our nanomaterial synthesis capabilities, laser 

processing techniques and spectroscopic phase conversion studies, and perovskite thin-film 

electrical characterization efforts. We also intend to initiate and pursue several new areas of 

focus: ICB: finalize construction of the large-scale reactor and pursue trials of continuous-flow 

production with automated control, and further investigate accelerated synthesis and improved 

throughput of pure and CeO2-doped BaTiO3 and BaSrTiO3 nanoparticles using MHz 

ultrasonication methods; Aerospace: conduct laser-scripted processing studies on the newly 

synthesized BaSrTiO3 and CeO2-doped nanoparticle thin-films, investigate the optical 
21

spectroscopy and photoemission characteristics of these novel material systems for optimized 

pyroelectric activation and process control, and explore the use of the IR absorbing layer for 

heating and patterned pyroelectric phase conversion of the underlying perovskite thin-film; ARL: 

perform electrical characterization and temperature-dependent pyroelectric measurements on 

ICB-provided functionalized BaTiO3 thin-films, and investigate the use of black silicon 

nanopillar structural layers for enhanced IR absorption.

6 Metrics for Year 2 Quarters 2 and 3 

6.1 Publications

1. Ould-Ely, T.; Niesz, K.; Luger, M.; Doherty, M.; Morse, D. E. First Large-scale Engineered 

Synthesis of BaTiO3 Nanopaticles Using Low Temperature Bioinspired Principles. Nature 

Protocols 2010, submitted. 

2. Livingston, F. E.; Sarney, W. L.; Little, J. W.; Olver, K. A.; Niesz, K.; Morse, D. E. Laserinduced Structuring of Bio-inspired Nanomaterials for Sensor Technology Applications, 

Proceedings of the Military Sensing Symposium. Joint Session on Materials/Detectors: 

Uncooled IR Detector and FPA Technology, Orlando, FL, Feb. 23, 2010. 

3. Niesz, K.; Morse, D. E. Sonication-accelerated Catalytic Synthesis of Oxide Nanoparticles. 

Nano Today April 2010, 5 (2), 99–105.

4. Livingston, F. E.; Helvajian, H. Laser Processing Architecture for Improved Material 

Processing. in Laser Processing of Materials: Fundamentals, Applications, and 

Developments, P. Schaaf, Ed., Springer Series Materials Science, 2010, invited book chapter 

in press. 

5. Sarney, W. L.; Little, J. W.; Livingston, F. E.; Niesz, K.; Cole, M. W.; Morse, D. E. Low 

Temperature Growth and Laser-induced Phase Transformation of Perovskite Oxide Films for 

Uncooled IR Detector Applications. Mater. Res. Soc. Symp. Proc. 2010, 1199.

6.2 Conferences and Symposia

1. Livingston, F. E.; Sarney, W. L.; Niesz, K.; Morse, D. E. Laser Direct-write Activation of 

Perovskite Nanoparticle Films for Thermal Detector Applications, National Defense 

Industrial Association (NDIA) – 11th Annual Science & Engineering Technology 

Conference/DoD Tech. Exposition, abstract accepted for presentation in Orlando, FL, Apr. 

2010. 
22

2. Livingston, F. E.; Sarney, W. L.; Niesz, K.; Little, J. W.; Olver, K. A.; Morse, D. E. Laser 

Tailoring of Bio-inspired Thin-films for Improved Sensitivity, Low-cost Uncooled IR 

Detector FPAs, 2010 Institute for Collaborative Biotechnologies (ICB) Army-Industry 

Collaboration Conference, UC Santa Barbara, CA, Mar. 3–4, 2010. 

3. Livingston, F. E.; Sarney, W. L.; Little, J. W.; Olver, K. A.; Niesz, K.; Morse, D. E. LaserInduced Structuring of Bio-inspired Nanomaterials for Sensor Technology Applications. 

invited talk at the Military Sensing Symposia (MSS) – Joint Session on Materials/Detectors: 

Uncooled IR Detector and FPA Technology, Orlando, FL, Feb. 23, 2010. 

4. Sarney, W. L.; Little, J. W.; Livingston, F. E.; Niesz, K.; Morse, D. E. Pyroelectric films 

Synthesized by Low-temperatures and Laser-processed for Uncooled Infrared Detector 

Applications. International Semiconductor Device Research Symposium, College Park, MD, 

Dec. 9, 2009. 

5. Sarney, W. L.; Little, J. W.; Livingston, F. E.; Niesz, K.; Cole, M. W.; Morse, D. E. Low 

Temperature Growth and Laser-induced Phase Transformation of Perovskite Oxide Films for 

Uncooled IR Detector Applications. Materials Research Society Fall Meeting, Boston, MA, 

Dec. 4, 2009. 
23

7. References 

1. Sarney, Wendy L. et al. Improved Sensitivity Low-cost Uncooled Infrared (IR) Detector 

Focal Plane Arrays; ARL-TR-4721; U.S. Army Research Laboratory: Adelphi, MD,

February 2009.

2. Sarney, Wendy L. et al. Progress in Biologically Inspired Pyroelectric Materials Growth for 

Improved Sensitivity, Lower-cost Uncooled IR Detector Focal Plane Arrays; ARL-TR-4770; 

U.S. Army Research Laboratory: Adelphi, MD, April 2009.

3. Sarney, Wendy L. et al. Bio-inspired Materials Research for Improved Sensitivity Low-cost 

Uncooled Infrared (IR) Detector Focal-plane arrays; ARL-TR-5172; U.S. Army Research 

Laboratory: Adelphi, MD, April 2010

4. Sarney, Wendy L. et al. Further Developments in Improved Sensitivity, Low-cost Uncooled 

IR Detector Focal Plane Arrays; ARL-TR-5389; U.S. Army Research Laboratory: Adelphi, 

MD, November 2010.

5. Wemple, S. H. Phys. Rev. B 1970, 2, 2679. 

6. Xu, J.; Durisin, D. P.; Auner, G. W. Proc. SPIE 2005, 5713, 305. 

7. Matsuda, H.; Kobayashi, N.; Kobayashi, T.; Miyazawa, K.; Kuwabara, M. J. Non-Cryst. 

Solids 2000, 271, 162. 

8. Kamalasanan, M. N.; Chandra, S.; Joshi, P. C.; Mansingh, A. Appl. Phys. Lett. 1991, 59, 

3547. 

9. Harizanov, O.; Harizanova, A.; Ivanova, T. Mater. Sci. Engineer. 2004, B106, 191. 

10. Golego, N.; Studenikin, S. A.; Cocivera, M. Chem. Mater. 1998, 10, 2000. 

11. Guo, H.; Liu, L.; Chen, Z.; Ding, S.; Lu, H.; Jin, K.-J.; Zhou, Y.; Cheng, B. Europhys. Lett. 

2006, 73, 110.
24

List of Symbols, Abbreviations, and Acronyms

AFM atomic force microscopy

ARL U.S. Army Research Laboratory 

BaTiO3 barium titanium oxide

BST barium strontium titanate

ICB Institute for Collaborative Biotechnologies

IR infrared

MBE molecular beam epitaxy

nm nanometer

PCD pulsed laser deposition

PFM piezoelectric force microscopy

PMMA polymethyl methocrylate

SEM scanning electron microscope

SHG second harmonic generation

Si silicon

UV ultraviolet

XRD x-ray diffraction

Y2Q2/3 year two, quarters two and three
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