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Sustainable Material Solutions for
Solar Energy Technologies
Processing Techniques and Applications
This page intentionally left blank
Solar Cell Engineering

Sustainable Material
Solutions for Solar
Energy Technologies
Processing Techniques and Applications

Edited by

Mariana Amorim Fraga

Instituto de Ciência e Tecnologia, Universidade Federal de São Paulo,
São José dos Campos, Brazil

Delaina Amos
University of Louisville, Louisville, KY, United States

Savas Sonmezoglu
Karamanoglu Mehmetbey University, Karaman, Turkey

Velumani Subramaniam
Department of Electrical Engineering (SEES),
Centro de Investigación y de Estudios Avanzados del IPN
(CINVESTAV-IPN), Mexico City, Mexico
Elsevier
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Contents

List of contributors xv
Preface xix

Section I
Trends in materials development for
solar energy applications
1. Bismuth-based nanomaterials for energy applications 3
Nichole C. Cates, Jessica C. Ramirez de la Torre, Sergio Aina,
M. Pilar Lobera and Marı́a Bernechea
1.1 Introduction 3
1.2 Photovoltaics 4
1.2.1 Solar Cell Operation 4
1.2.2 Nanoengineering 6
1.2.3 Bismuth-Based Nanomaterials 7
1.2.4 Summary 9
1.3 Thermoelectric devices 9
1.3.1 Thermoelectric Devices Operation 9
1.3.2 Nanoengineering 11
1.3.3 Bi-Based Nanomaterials 12
1.3.4 Summary 16
1.4 Batteries & Supercapacitors 16
1.4.1 Battery Operation 16
1.4.2 Supercapacitor Operation 17
1.4.3 Bismuth-Based Electrodes 17
1.4.4 Nanoengineering 18
1.4.5 Coating or Mixing with Conductive Materials 20
1.4.6 Bismuth Perovskite Supercapacitors 21
1.4.7 Summary 21
1.5 Solar-hydrogen production 22
1.5.1 Fundamentals of photocatalysis for hydrogen production 22
1.5.2 Nanoengineering 24
1.5.3 Bi-based nanomaterials 24
1.5.4 Summary 29
1.6 Conclusions 29
Acknowledgements 30
References 30

v
vi Contents

2. Emergent materials and concepts for solar cell

applications 37
Marı́a Dolores Perez and Juan Plá
2.1 Introduction 37
2.2 Perovskite solar cells 40
2.2.1 Historical review 40
2.2.2 Solar cells 41
2.2.3 Stability 45
2.2.4 Scaling up and possibilities for commercialization 49
2.3 III
V semiconductor materials for multijunction solar cells
applications 50
2.3.1 Historical review 50
2.3.2 Some basics of multijunction solar cells 53
2.3.3 III
V materials for photovoltaic applications 55
2.3.4 Selected examples 58
2.3.5 Discussion 61
2.4 Final remarks and future perspectives 62
References 63

3. Novel dielectrics compounds grown by atomic layer

deposition as sustainable materials for chalcogenides
thin-films photovoltaics technologies 71
William Chiappim Junior, Leandro X. Moreno, Rodrigo Savio Pessoa,
António F. da Cunha, Pedro M.P. Salomé and Joaquim P. Leitão
3.1 Introduction 71
3.2 Atomic layer deposition technique 78
3.2.1 Requirements for ideal precursors and atomic layer
deposition signature quality 79
3.2.2 Commercial and research tools 82
3.3 Atomic layer deposition applied on chalcogenides thin films
technologies 84
3.3.1 Absorber layers: Cu(In,Ga)Se2, Cu2ZnSnS4, and
Cu2ZnSn(S,Se)4 85
3.3.2 Sustainable buffer layers based on atomic layer deposition 87
3.3.3 Sustainable passivation layers based on atomic layer
deposition 88
3.4 Final remarks 89
Acknowledgments 90
References 90

4. First principles methods for solar energy harvesting

materials 101
J.J. Rı́os-Ramı́rez and Velumani Subramaniam
4.1 Introduction 101
 Contents vii

4.2 Fundamental concepts 103

4.2.1 Crystalline representation 103
4.2.2 The multielectron system 107
4.2.3 The variational principle 111
4.2.4 The universal functional of the density 113
4.2.5 The auxiliary Kohn-Sham system 116
4.3 Selected materials with solar energy harvesting
implementations 118
4.3.1 The input file 118
4.3.2 A supercell of zinc oxide 121
4.3.3 Structural stability of FAPbI3 perovskites 122
4.3.4 Charge order and half metallicity of Fe3O4 122
4.3.5 Optimization of anatase titanium dioxide 123
4.3.6 A conventional and a reduced representation of mBiVO4 125
4.3.7 A template structure for chalcopyrite 126
4.4 Conclusion 127
References 127

Section II
Sustainable materials for photovoltaics
5. Introduction to photovoltaics and alternative
materials for silicon in photovoltaic energy conversion 131
Ganesh Regmi and Velumani Subramaniam
5.1 Introduction 131
5.2 Current status of photovoltaics 133
5.3 Fundamental properties of photovoltaics semiconductors 136
5.3.1 Crystal structure of semiconductors 136
5.3.2 Energy band structure 137
5.3.3 Density of energy states 139
5.3.4 Drift-motion due to the electric field 142
5.3.5 Diffusion-due to a concentration gradient 143
5.3.6 Absorption coefficient 144
5.4 Physics of solar cell 145
5.4.1 Homojunction and heterojunction structure 146
5.4.2 p-n junction under illumination 147
5.4.3 I-V equations of solar cell 149
5.5 Categories of the photovoltaic market 151
5.6 Commercialization of Si solar cells 152
5.7 Status of alternative photovoltaics materials 153
5.8 Thin film technology 154
5.9 Material selection in thin film technology 157
5.10 Thin film deposition techniques 158
5.10.1 Physical deposition 158
5.10.2 Chemical deposition 160
viii Contents

5.11 Copper indium gallium selenide-based solar cell 162

5.11.1 Alkali metal postdeposition treatment on copper
indium gallium selenide based solar cells 163
5.12 Cadmium telluride solar cells 164
5.13 Multijunction solar cells 165
5.14 Emerging solar cell technologies 165
5.14.1 Organic solar cells 166
5.14.2 Dye-sensitized solar cells 166
5.14.3 Perovskite solar cells 168
5.14.4 Quantum dot solar cells 168
5.15 Summary, conclusions, and outlook 169
Acknowledgment 170
References 170

6. An overview on ferroelectric photovoltaic materials 175

Savita Sharma
6.1 Overview 175
6.2 Ferroelectric materials 176
6.3 Photovoltaic effect 178
6.3.1 Mechanism of ferroelectric photovoltaic 179
6.3.2 History and current status of ferroelectric photovoltaic 186
6.4 Barium titanate 187
6.4.1 Crystal structure 187
6.4.2 Dielectric properties 190
6.4.3 Ferroelectric phenomena in BaTiO3 190
6.4.4 Optical properties 191
6.4.5 Various techniques of depositing BaTiO3 thin film 191
6.4.6 Potential applications of BaTiO3 192
6.5 Bismuth ferrite 194
6.6 Conclusion 195
Acknowledgments 196
References 196

7. Nanostructured materials for high efficiency solar cells 201

Daniel N. Micha, Roberto Jakomin, Rudy M.S. Kawabata,
Mauricio P. Pires, Fernando A. Ponce and Patrı́cia L. Souza
7.1 Introduction 201
7.2 Nanostructures and quantum mechanics 203
7.3 Quantum wells in solar cells 205
7.4 Quantum wires (nanowires) in solar cells 210
7.5 Quantum dots in solar cells 214
7.5.1 InAs quantum dots on GaAs 216
7.5.2 In(Ga)As or InAsP quantum dots on wide bandgap
material barriers 221
 Contents ix

7.6 Conclusions 222

Acknowledgments 223
References 223

8. Crystalline-silicon heterojunction solar cells with

graphene incorporation 229
Recep Zan, Ali Altuntepe, Tolga Altan and Ayse Seyhan
8.1 Heterojunction solar cells and graphene 229
8.1.1 Heterojunction solar cells 229
8.1.2 Graphene 232
8.2 Fabrication of silicon heterojunction solar cell 234
8.2.1 Surface patterning and surface cleaning 235
8.2.2 Deposition of a-silicon:H layers 237
8.2.3 Deposition of transparent conductive oxide 240
8.2.4 Metallization 242
8.2.5 Thermal treatment 243
8.3 Synthesis of graphene 244
8.3.1 Incorporating graphene into silicon heterojunction
solar cells 249
8.4 Conclusion 250
Acknowledgment 251
References 251

9. Tin halide perovskites for efficient lead-free

solar cells 259
Giuseppe Nasti, Diego Di Girolamo and Antonio Abate
9.1 Introduction 259
9.2 Halide perovskite solar cells: why tin? 263
9.2.1 Perovskite structure 263
9.2.2 Carrier transport and tin halide perovskite defects 266
9.2.3 Tin perovskite bandgap 267
9.2.4 Tin oxidation 269
9.2.5 Tin toxicity 271
9.3 ASnX3: a brief historical excursus 272
9.4 Toward efficient and stable ASnX3 PSCs 274
9.4.1 Additives 274
9.4.2 Passivation 277
9.4.3 Low dimensional perovskites 279
9.4.4 Solvent 280
9.5 Conclusion 281
References 281
x Contents

Section III
Sustainable materials for photocatalysis
and water splitting
10. Photocatalysis using bismuth-based
heterostructured nanomaterials for visible light
harvesting 289
Araceli Romero-Nuñez, K.T. Drisya, Juan Carlos Durán-Álvarez,
Myriam Solı́s-López and Velumani Subramaniam
10.1 Introduction 289
10.2 Fundamentals of heterogeneous photocatalysis 291
10.2.1 Heterogeneous photocatalysis applied to
environmental engineering processes 294
10.2.2 Factors affecting the photocatalytic process 295
10.2.3 Insights of physicochemical characterization of
nanophotocatalysts 297
10.3 Bismuth-based heterostructures for photocatalytic
applications 299
10.3.1 Semiconductor-semiconductor heterostructures
using bismuth-based materials 301
10.3.2 General strategies for synthesis of bismuth-based
semiconductors 303
10.3.3 Applications of bismuth-based heterostructures 309
10.4 Conclusions 320
Acknowledgments 321
References 321

11. Recent advances in 2D MXene-based heterostructured

photocatalytic materials 329
Sudeshna Das Chakraborty, Pallab Bhattacharya and
Trilochan Mishra
11.1 Introduction 329
11.2 Synthesis of 2D-MXenes 331
11.2.1 Functionalization and electronic properties of
MXene 333
11.3 Photocatalytic applications 334
11.3.1 H2 evolution by H2O splitting 336
11.3.2 Photocatalytic CO2 reduction to fuel 345
11.3.3 Environmental applications 347
11.4 Conclusion and future prospects 355
Acknowledgments 356
References 356
 Contents xi

12. Atomic layer deposition of materials for

solar water splitting 363
Rodrigo Savio Pessoa, William Chiappim Junior and
Mariana Amorim Fraga
12.1 Introduction 363
12.2 Solar energy 366
12.3 Photoelectrochemical cells 367
12.4 Hydrogen generation from water photoelectrolysis 368
12.5 Materials for photoelectrode 369
12.6 Atomic layer deposition technique: process and equipment 373
12.6.1 Atomic layer deposition process 373
12.6.2 Atomic layer deposition reactors: types and
characteristics 375
12.7 Final remarks 376
Acknowledgments 376
References 376

Section IV
Sustainable materials for thermal energy systems
13. Solar selective coatings and materials for
high-temperature solar thermal applications 383
Ramón Escobar Galindo, Matthias Krause, K. Niranjan and
Harish Barshilia
13.1 Introduction 383
13.1.1 Concentrated solar power: facts 383
13.1.2 Concentrated solar power: basics 388
13.2 CSP efficiency considerations: the concept of solar selectivity 392
13.3 State-of-the-art review of solar absorber surfaces and
materials for high-temperature applications ( . 565 C in air) 395
13.3.1 Absorber paints 395
13.3.2 Solar selective coatings 397
13.3.3 Volumetric receivers 402
13.4 Current trends and issues 405
13.4.1 Durability studies of solar absorbers 405
13.4.2 Lack of standardized characterization protocols 407
13.5 Roadmap for concentrated solar power absorbing
surfaces and materials 409
13.5.1 Alternative concentrated solar power absorbing
surfaces: selectively solar-transmitting coatings 409
13.5.2 Industrialization of high-temperature solar selective
coatings 413
Acknowledgments 417
References 418
xii Contents

14. Applications of wastes based on inorganic salts as

low-cost thermal energy storage materials 429
Svetlana Ushak, Yanio E. Milian, Paula E. Marı́n and Mario Grageda
14.1 Introduction 429
14.2 Thermal energy storage 431
14.2.1 Sensible, latent and thermochemical heat storage 431
14.2.2 Basic concepts for thermal energy storage materials 434
14.2.3 Overview of thermal energy storage system types 438
14.2.4 Comparison of energy storage density for different
thermal energy storage materials 439
14.3 Overview of industrial waste studied as thermal energy
storage materials 440
14.4 Inorganic salt-based products and wastes as low-cost
materials for sustainable thermal energy storage 442
14.4.1 Availability and abundance of inorganic salts in
Northern Chile 442
14.4.2 Economic analysis of inorganic salts as low-cost
thermal energy storage materials 444
14.4.3 State-of-art of currently proposed by-products and
wastes as thermal energy storage materials 446
14.5 Challenges for the application of waste and by-products in
thermal energy storage systems 453
14.5.1 Proposed uses of wastes as thermal energy storage
materials 453
14.5.2 Challenges for the application of inorganic salt-based
wastes in thermal energy storage systems 455
14.5.3 Optimization of thermal properties of thermal energy
storage materials based on inorganic salt wastes 456
14.6 Conclusion 461
References 461

15. Nanoencapsulated phase change materials for solar

thermal energy storage 467
Jyoti Saroha, Sonali Mehra, Mahesh Kumar,
Velumani Subramaniam and Shailesh Narain Sharma
15.1 Introduction 467
15.1.1 Selection criteria of phase change materials 470
15.1.2 Working principle of phase change material 473
15.1.3 Encapsulation in phase change materials 474
15.1.4 Advantages of micro or nanoencapsulation of
phase change material 476
15.2 Brief review of the work done 476
15.3 Results and discussion 479
15.4 Applications 483
 Contents xiii

15.4.1 Need for phase change material-based solar air

heaters 484
15.4.2 Need for phase change material-based building
materials for rural houses 486
15.4.3 Need for phase change material-based textiles 488
15.5 Challenges ahead 490
15.6 Conclusions 490
Acknowledgments 491
References 491
Further reading 494

Section V
Sustainable carbon-based and biomaterials for
solar energy applications
16. Carbon nanodot integrated solar energy devices 497
Melis Özge Alaş and Rükan Genç
16.1 Introduction 497
16.2 Carbon nanodot integrated solar energy devices 500
16.2.1 Dye-sensitized solar cells 500
16.2.2 Quantum dot solar cells 509
16.2.3 Organic solar cells 511
16.2.4 Polymer solar cells 515
16.2.5 Perovskite solar cells 519
16.3 Summary and future aspects 524
Acknowledgments 529
References 529

17. Solar cell based on carbon and graphene

nanomaterials 537
Abdellah Henni, Nesrine Harfouche, Amina Karar and
Djamal Zerrouki
17.1 Introduction 537
17.2 Carbon and its derivatives 538
17.2.1 Fullerene 538
17.2.2 Carbon nanotube 540
17.2.3 Graphene 540
17.3 Solar cells based on carbon nanomaterials 541
17.3.1 Carbon in dye-sensitized solar 541
17.3.2 Carbon in organic solar cells 543
17.3.3 Carbon in perovskite solar cells 544
17.4 Challenges and prospects 547
References 549
xiv Contents

18. Sustainable biomaterials for solar energy technologies 557

Yakup Ulusu, Numan Eczacioglu and Isa Gokce
18.1 Introduction 557
18.2 Structural properties of biomaterials 558
18.3 Biomaterials used in biophotovoltaics 562
18.3.1 Living organism based solar cell systems 563
18.3.2 Light-harvesting proteins 570
18.3.3 Natural pigments 575
References 584

19. Bioinspired solar cells: contribution of biology to

light harvesting systems 593
B. Gopal Krishna and Sanjay Tiwari
19.1 Introduction 593
19.2 Methodologies for engineered biomimicry 595
19.2.1 Bioinspiration 595
19.2.2 Biomimetic 596
19.2.3 Bioreplication 597
19.3 Bioinspired solar cells 597
19.4 Bioinspired structures and organisms 601
19.4.1 Dyes 601
19.4.2 Wettability and superhydrophobic dyes 603
19.4.3 Organisms 603
19.5 Biological processes for bioinspiration 611
19.5.1 Photosynthesis 611
19.5.2 Cyanobacteria 614
19.5.3 Bioinspired chromophores 616
19.6 Physics in biological systems 616
19.6.1 Coherence effects in biological systems 616
19.6.2 Excitation energy transfer 617
19.6.3 Charge transfer 618
19.7 Structures 620
19.7.1 Origami structures 620
19.7.2 Graphene 620
19.7.3 Multijunction solar cells 620
19.7.4 Perovskite solar cells 620
19.7.5 Silicon-based solar cell 621
19.7.6 Dye-sensitized solar cell technology 622
19.7.7 Thin film solar cell 623
19.8 Conclusions 623
References 625

Index 633
List of contributors

Antonio Abate Department of Chemical, Materials and Production Engineering,

University of Naples Federico II, Naples, Italy
Sergio Aina Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-
Universidad de Zaragoza, Zaragoza, Spain; Department of Chemical and
Environmental Engineering (IQTMA), University of Zaragoza, Zaragoza, Spain
Melis Özge Alaş Chemical Engineering Department, Faculty of Engineering, Mersin
University, Mersin, Turkey
Tolga Altan Nanotechnology Application and Research Center, Niğde Ömer
Halisdemir University, Niğde, Turkey; Department of Mechanical Engineering,
Niğde Ömer Halisdemir University, Niğde, Turkey
Ali Altuntepe Nanotechnology Application and Research Center, Niğde Ömer
Halisdemir University, Niğde, Turkey
Harish Barshilia Nanomaterials Research Laboratory, Surface Engineering Division,
CSIR-National Aerospace Laboratories, Bangalore, India
Marı́a Bernechea Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-
Universidad de Zaragoza, Zaragoza, Spain; Department of Chemical and
Environmental Engineering (IQTMA), University of Zaragoza, Zaragoza, Spain;
Networking Research Center on Bioengineering, Biomaterials and Nanomedicine,
Madrid, Spain; ARAID, Government of Aragon, Zaragoza, Spain
Pallab Bhattacharya Functional Material Group, AMP Division, CSIR-National
Metallurgical Laboratory, Jamshedpur, India
Nichole C. Cates Smart Material Solutions, Inc, Raleigh, NC, United States of
America
William Chiappim Junior i3N and Department of Physics, University of Aveiro,
Aveiro, Portugal; Plasmas and Processes Laboratory, Aeronautics Institute of
Technology, São José dos Campos, Brazil
António F. da Cunha i3N and Department of Physics, University of Aveiro, Aveiro,
Portugal
Sudeshna Das Chakraborty Functional Material Group, AMP Division, CSIR-
National Metallurgical Laboratory, Jamshedpur, India
K.T. Drisya Departamento de Ingenierı́a Eléctrica, Centro de Investigación y de
Estudios Avanzados del Instituto Politécnico Nacional, Mexico City, Mexico
Juan Carlos Durán-Álvarez Instituto de Ciencias Aplicadas y Tecnologı́a,
Universidad Nacional Autónoma de México, Mexico City, Mexico

xv
xvi List of contributors

Numan Eczacioglu Department of Bioengineering, Faculty of Engineering,

Karamanoglu Mehmetbey University, Karaman, Turkey
Mariana Amorim Fraga Institute of Science and Technology, Federal University of
São Paulo, São José dos Campos, Brazil
Ramón Escobar Galindo Applied Physics I Department, Higher Polytechnic School
(EPS), University of Seville, Spain
Rükan Genç Chemical Engineering Department, Faculty of Engineering, Mersin
University, Mersin, Turkey
Diego Di Girolamo Department of Chemical, Materials and Production Engineering,
University of Naples Federico II, Naples, Italy
Isa Gokce Department of Bioengineering, Faculty of Natural Sciences and
Engineering, Tokat Gaziosmanpasa University, Tokat, Turkey
B. Gopal Krishna Photonics Research Laboratory, School of Studies in Electronics
& Photonics Pt. Ravishankar Shukla University, Raipur, India
Mario Grageda Center for Advanced Study of Lithium and Industrial Minerals
(CELiMIN), University of Antofagasta, Antofagasta, Chile
Nesrine Harfouche Polymer Materials Interfaces Marine Environment, University of
South Toulon, Toulon, France
Abdellah Henni Laboratory Dynamic Interactions and Reactivity of Systems, Kasdi
Merbah University, Ouargla, Algeria
Roberto Jakomin Campus Duque de Caxias, Universidade Federal do Rio de
Janeiro, Duque de Caxias, Brazil
Amina Karar Laboratory Dynamic Interactions and Reactivity of Systems, Kasdi
Merbah University, Ouargla, Algeria
Rudy M.S. Kawabata Semiconductor Laboratory, Pontifı́cia Universidade Católica
do Rio de Janeiro, Rio de Janeiro, Brazil
Matthias Krause Helmholtz-Zentrum Dresden-Rossendorf, Institute for Ion Beam
Physics and Materials Research, Dresden, Germany
Mahesh Kumar Council of Scientific and Industrial Research (CSIR)-National
Physical Laboratory (NPL), New Delhi, India; Academy of Scientific and
Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh, India
Joaquim P. Leitão i3N and Department of Physics, University of Aveiro, Aveiro,
Portugal
M. Pilar Lobera Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-
Universidad de Zaragoza, Zaragoza, Spain; Department of Chemical and
Environmental Engineering (IQTMA), University of Zaragoza, Zaragoza, Spain;
Networking Research Center on Bioengineering, Biomaterials and Nanomedicine,
Madrid, Spain
Paula E. Marı́n Sustainable Thermal Energy Technologies (STET), University of
Warwick, Coventry, United Kingdom
 List of contributors xvii

Sonali Mehra Council of Scientific and Industrial Research (CSIR)-National

Physical Laboratory (NPL), New Delhi, India; Academy of Scientific and
Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh, India
Daniel N. Micha Department of Physics, Centro Federal de Educação Tecnológica
Celso Suckow da Fonseca, Petrópolis, Brazil
Yanio E. Milian Center for Advanced Study of Lithium and Industrial Minerals
(CELiMIN), University of Antofagasta, Antofagasta, Chile
Trilochan Mishra Functional Material Group, AMP Division, CSIR-National
Metallurgical Laboratory, Jamshedpur, India
Leandro X. Moreno Department of Physics, Institute of Geosciences and Exact
Sciences (IGCE), São Paulo State University “Júlio de Mesquita Filho” (Unesp),
Rio Claro, Brazil
Giuseppe Nasti Department of Chemical, Materials and Production Engineering,
University of Naples Federico II, Naples, Italy
K. Niranjan Nanomaterials Research Laboratory, Surface Engineering Division,
CSIR-National Aerospace Laboratories, Bangalore, India
Marı́a Dolores Perez Institute for Nanoscience and Nanotechnology (INN)—
National Atomic Energy Commission (CNEA)—National Council for Scientific
and Technical Research (CONICET), Buenos Aires, Argentina; Solar Energy
Department— National Atomic Energy Commision, Av. General Paz 1499, San
Martin, Buenos Aires, Argentina
Rodrigo Savio Pessoa Plasmas and Processes Laboratory, Aeronautics Institute of
Technology, São José dos Campos, Brazil
Mauricio P. Pires Institute of Physics, Universidade Federal do Rio de Janeiro, Rio
de Janeiro, Brazil
Juan Plá Institute for Nanoscience and Nanotechnology (INN)—National Atomic Energy
Commission (CNEA)—National Council for Scientific and Technical Research
(CONICET), Buenos Aires, Argentina; Solar Energy Department— National Atomic
Energy Commision, Av. General Paz 1499, San Martin, Buenos Aires, Argentina
Fernando A. Ponce Department of Physics, Arizona State University, Tempe, AZ,
United States
Jessica C. Ramirez de la Torre Instituto de Nanociencia y Materiales de Aragón
(INMA), CSIC-Universidad de Zaragoza, Zaragoza, Spain; Department of
Chemical and Environmental Engineering (IQTMA), University of Zaragoza,
Zaragoza, Spain
Ganesh Regmi Department of Electrical Engineering (SEES), Centro de
Investigación y de Estudios Avanzados del IPN (CINVESTAV-IPN), Mexico
City, Mexico
J.J. Rı́os-Ramı́rez Departamento de Ingenierı́a Eléctrica (SEES), Centro de
Investigación y de Estudios Avanzados del Instituto Politécnico Nacional
(CINVESTAV-IPN), Ciudad de México, Mexico
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her cheek, and said:

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How many kisses do you suppose he had then? As for Mrs. Sullivan,
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 NOBLE AND TRICKSY.

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the funny thing I am going to tell you, actually happened.

There was nothing that the little scamp named "Noble" liked better
than to have a race with old Tricksy around the great trees on the
lawn. Yes, perhaps there was one thing that he liked almost as well,
and that was, to curl himself on a certain cushion that before he
came, had been the large dog's special property.

So sure as the old dog left it for a minute to do an errand, or to

attend to any of his duties, up the little scamp would jump and be in
possession. Good old Tricksy stood it patiently a good many times,
but at last one day he evidently thought out a way to manage the
little new comer. It was just after a hearty dinner, and it was a chilly
day, and a cosy nap on the warm cushion, I suppose, looked most
inviting to both dogs. The little one was ahead, as usual, and the old
dog sat clown by the stove to think about it. At last he got up, moved
gravely towards the door leading to the lawn, then turned around to
the little dog and said as plainly as dog-language would admit:

"Come on, then, if you want a race."

 TRICKSY.

Down jumped the little dog in a perfect flutter of delight, and wagged
his tail, and barked his short, sharp barks that said "Oh, good, good!"
and ran to the door.

What did our grave old dog do but turn around very quickly, spring to
the bench behind the stove, curl himself on the cushion, and go to
sleep, leaving the disappointed younger one to bear the loss of his
frolic and his cushion, as best he might!

"He has earned his name!" somebody said, laughing. "O, Tricksy,
Tricksy! We can never say you ought to be called 'Noble' any more."

But what do you think Robbie did? Instead of being delighted with
the sharpness of his dear old dog, he burst into tears.

"Why, Robbie!" mamma said. "What is the matter?"

Then Robbie wailed forth his heart-breaking question:

"Was it wicked, mamma? Tricksy didn't know any better; he is only a

dog."

"Of course it was wicked!" Nelson declared in his most teasing tone.
"My good little Noble wouldn't think of doing such a cheating thing."

NOBLE.
Whether mamma wanted to comfort Robbie or whether she thought
Nelson needed the lesson; or whether it was a little of both reasons
that made her speak just then, I will not stop to tell you, but what she
said was:

"He may have been led astray by bad example. I wonder if it can be
possible that he saw a boy take his slate and book under his arm
yesterday and walk towards the stairs as if he were going to the
library to study, then dodge out at the side door, hide his books
under a rose-bush, and run off to play marbles with the boys?"

Not a word said Nelson; his cheeks grew red, and he looked down
and fumbled with his watch-chain. Do you think his mother could
have meant him?
 GIESSBACH.

THE two girls squealed with delight over the picture. "Just see! three
falls, one on top of the other!" declared Fannie. "Oh dear me! How I
should like to see them! You can't tell any thing by looking at a
picture."

Tom came and looked over their shoulders.

"Where is the thing?" he asked.

"Why, it is that wonderful Giessbach fall in Switzerland that Mr.

Warder told us about. He said it was just the loveliest view in all
Switzerland; and he promised aunt Kate a picture of it. But pictures
are the most unsatisfactory things! I want to see the color of the
rocks, and the little ferns and bushes growing about, and hear the
water dashing. But I don't suppose I ever shall see or hear any such
things. I expect to fly, just as much as I expect to go to Switzerland."

"You needn't go to Switzerland to see a grand waterfall," declared

Tom. "I don't believe Giessbach with its horrible name, is any finer
than Cheyenne Cañon fall, that I stood under only last week. I tell
you, Fannie, that was a sight! Three falls, distinct from each other,
yet all tumbling into one at the bottom, and making the grandest kind
of white foam. I stood as close to it as I do to you, and the spray
came all over my face. Then we went up the mountain and looked
down on it all. How many falls do you think we saw then? Seven of
them, all roaring down together. That was a sight to remember, and
we didn't have to go abroad for it, either. You can just make up your
mind, Fannie, that there are about as grand things to look at in our
own country as can be found anywhere."
But Fannie was in the mood to grumble:

"Oh, well, one might as well go abroad as to go to Colorado; I don't

expect ever to be able to go there, either."

"Humph!" said Tom. "Neither did I expect to; I could have imagined
myself in the moon as well as in Colorado, three weeks before I
went; yet I went, and so may you. People can't ever tell what may
happen to them. You just remember that when you do go, there is
one place to see; the falls of Cheyenne Cañon. People who have
seen both, say that there is nothing grander in Switzerland than they
get up in that cañon."

Cora, meantime, had been listening in silence, gazing with

thoughtful, far-away eyes at the picture. At last she spoke:

"Tom, what did you think of when you stood looking up at the
wonderful foamy water coming down from so high a place?"

Tom's face flushed a little.

"People think different things," he said, laughing. "As I stood there

looking at it, I said, 'What a grand place that would be for a shower
bath. I'd just like to go and stand under it, and take a good one.'
There was a little chap stood by me, a pale-faced fellow with blue
eyes, who had taken off his cap and stared up without speaking, for
ten minutes. Just then he turned to me and said:"

"'I've been thinking how easy it must be for God to make wonderful
things! Here he has made all this white water and tumbled it down
from away up in heaven—that is the way it looks—just for the sake
of giving these old still rocks something bright to play with.'"

"Wasn't that a poetical thought? Sounds like you, Cora. It made me

think of you at the time."
 A BIT OF LOGIC.

RUFUS lay at full length on the sofa, and puffed a cigar, back parlor
though it was; when Mr. Parker reminded him of it, he said there
were no ladies present, and puffed away. Between the puffs he
talked:

"There is one argument against foreign mission work which is

unanswerable; the country cannot afford it. Two millions and a half of
money taken out this year, and sent to the cannibals, or somewhere
else. No country can stand such a drain as that upon it, with
everything else it has to do. Foreign missions are ruinously
expensive."

The two young sisters of Rufus, Kate and Nannie, stood on the
piazza and laughed.

"O Rufus!" said Kate. "You won't take a prize in college for logic, I'm
sure."

"What do you mean, little monkey? And 'what do you know about
logic?"

"More than you do I should think. Just imagine the country not being
able to afford two millions and a half for missions, when just a few
years ago it paid over four millions for Havana cigars. Have you
thought of that, Rufus?"

"And I wonder how much champagne is a bottle?" chimed in Nannie.

"How much is it, Rufus? You know about ten million bottles are used
every year. And oh! why, Rufus, don't you know that we spend about
six millions for dogs! Something besides foreign missions might be
given up to save money, I should think."

"Where did you two grow so wise? Where did you get all those
absurd items?"

"We got them at the Mission Band; Kate is secretary, and I'm
treasurer, and these figures were all in the dialogue that Dr.
Stephens wrote for us to recite. If you choose to call what he says
absurd, I suppose you can; but he is a graduate from a college, and
a theological seminary, beside. I mean to tell him that you think two
millions and a half for foreign missions, will ruin the country; I want to
hear him laugh." And then the two girls laughed merrily.

"You needn't tell him anything about it," said Rufus sharply. After the
girls ran away, he added thoughtfully:

"How fast girls grow up! I thought those two were children; and here
they are with the Mission Bands, and their large words about
'secretaries and treasurers.'"

"And their embarrassing facts about money," interrupted Mr. Parker.

"Those girls had the best of the argument, Rufus;" and then he too
laughed.
 INTERLAKEN.

INTERLAKEN means between the lakes, and is the name of a

village in Switzerland. It is situated between two lakes called Thun
and Brienz. All you geography scholars will be able to turn to it in
your minds, or if not so, on your maps. The village is in a plain and
on the river Aare, and you have in the picture a view of the bridge
across the river. The people who live at Interlaken lead quite
uneventful lives, gaining the means of living by carving toys in all
sorts of quaint devices, which are sold in the shops which line the
principal streets. The wonderful scenery brings large numbers of
visitors to the place, and these visitors are the purchasers of the
curiosities of the shops.

Large quantities of Swiss lace and Swiss carving find its way to the
United States in the trunks of American travellers; and I have no
doubt that when you visit Europe you will bring away a quantity of
the work of these same Interlaken lace-makers and carvers.
However you may set your face against the folly, you will be sure to
find some things which you must have.
 INTERLAKEN.

The scenery in this valley is among the finest in Switzerland. From

the windows of some of the pensions or boarding-houses, you may
get a view of the celebrated "Jungfrau." Do you know that Jungfrau
means "the maiden?" There seems to be a dispute as to the origin of
the name. Some say it was given to this lofty peak because of the
spotless purity of appearance on account of the unsullied snow
which always covers its summit. The view which you get of the
Jungfrau at Interlaken is through an opening in the range of lower
mountains that lie at the base of the grand old mountain itself, which
is nearly fourteen thousand feet high. I believe that the first to reach
the top was a party of natives of the valley, in 1828.

Soon after a scientific expedition, accompanied by the renowned

Agassiz, made the ascent. You will find within a few miles of the
village of Interlaken many points of wild and picturesque beauty, and
you will want to visit the waterfall Staubbach, which means "sky
born," and is one of the highest in Europe.
 WHITE AND CLEAN.

"C-H-E-S-T-E-R!" It was his mother's voice, and it rang out from her
room in the second story. "Only half an hour until school-time."

"Yes'm," shouted Chester. "I'll be there." But he bent over the tub and
rubbed Sport so fiercely that he howled.

"Keep still, sir," said Chester. "A dog who can't stand being washed
shouldn't have white feet and a white nose; I'm not going to have you
trotting around looking so horrid dirty as you have for a week. Look
here, sir; don't you try to bite me. If you do, you'll get a whipping. I'm
in a hurry."

Rub, rub, souse, souse!

Poor Sport shivered, and howled, and struggled, and looked as

though he would never feel equal to his name again: but Chester
splashed away.

His mother opened her window again.

"My son, you shouldn't have begun with the dogs this morning; you
knew it was late. Let Sport go at once, and leave Beauty until to-
night."
 THE CAUSE OF A POOR ARITHMETIC LESSON.

"O, mamma! I cannot possibly leave Beauty. He looks worse than

Sport did."

"Can't help it, my boy. You will be late to school, and have a poor
lesson."

"I'm coming, mamma, right away."

Out went Sport to the piece of carpet with which he was rubbed; glad
was he to get out of that horrible tub at any cost. But in went Beauty,
and the soaping, and howling, and splashing, and scolding went on
again. Chester worked fast, no doubt—although I suppose Beauty
did not think so—but before his work was half done, the window of
his mother's room went up with a click that meant business.

"Chester, put that dog on the ground and come here immediately."
Which Chester immediately did, shaking the soapy drops from him
as he went.

I suppose you are not surprised to hear that half an hour afterwards,
in the arithmetic class, he said that seven times eight was ninety-
four, and insisted that such was the case, even after half the girls in
the class were laughing over it. This is about a specimen of the way
in which he knew his entire lesson. Of course he sat gloomily in his
seat during recess, with his arithmetic upside down.

"Chester," his teacher asked, "how is it that you failed on your lesson
this morning?"

"I didn't have time to study it, sir."

"Is that so?" said Mr. Pierson. He thought a great deal of Chester,
who, to tell you the truth, generally had his lesson. His mother often
had trouble about it, but the teacher rarely had. "I think I'll have to
excuse you," his teacher said kindly, "if you really had not the time to
learn it. You may make it up to-morrow."

And Chester went to the playground with a hurrah on his lips. He

seemed to be very happy the rest of the day. When he went home,
he was full of play, and greeted the dogs with words of praise for
keeping themselves looking so well.

"Your nose is almost as clean as it was this morning, when you

fought so hard against my washing it, you ungrateful fellow!" he said
to Sport.

A very happy boy he was all the evening. He went to bed happy. He
knelt down in his white night-suit and said "Our Father," and then
hopped into bed with a whistle, and the next minute was asleep.

Poor Chester! Why? Oh, to be a boy who disobeyed his mother, and
told two falsehoods, and yet to think so little of it all that he could go
to bed whistling, without even having asked to be forgiven, is to be a
boy who needs pity.
Two falsehoods? Yes, indeed! Didn't he say to his mother, "I'm
coming right away," and go on with his work that she had directed
him to leave? Didn't he tell the teacher he "hadn't time," when the
truth would have been that he chose to take the time which belonged
to the arithmetic for something else?

White and clean! Oh, yes, that is what the dogs were; clean as to
their consciences for that matter, if they had any; for I believe they
acted as well as they knew how all that day. But how was it with
Chester's heart?
 "BOY WANTED."

PEOPLE laughed when they saw the sign again. It seemed to be

always in Mr. Peters' window. For a day or two, sometimes for only
an hour or two, it would be missing, and passers-by would wonder
whether Mr. Peters had at last found a boy to suit him; but sooner or
later, it was sure to appear again.

"What sort of a boy does he want, anyway?" one and another would
ask. And then they would say to each other, that they supposed he
was looking for a perfect boy, and in their opinion, he would look a
good while before he found one. Not that there were not plenty of
boys—as many as a dozen used sometimes to appear in the course
of a morning, trying for the situation. Mr. Peters was said to be rich
and boys were very anxious to try to suit him. "All he wants is a
fellow to run of errands; it must be easy work and sure pay." This
was the way they talked to each other. But Mr. Peters wanted more
than a boy to run of errands. John Simmons found that out, and this
was the way he did it. He had been engaged that very morning, and
had been kept busy all the forenoon, at pleasant enough work, and
although he was a lazy fellow, he rather enjoyed the place.

It was towards the middle of the afternoon that he was sent up to the
attic, a dark, dingy place, inhabited by mice and cobwebs.

"You will find a long deep box there," said Mr. Peters, "that I want to
have put in order. It stands right in the middle of the room, you can't
miss it."

John looked doleful. "A long deep box, I should think it was!" he told
himself, as the attic door closed after him. "It would weigh most a
ton, I guess; and what is there in it? Nothing in the world but old
nails, and screws, and pieces of iron, and broken keys and things;
rubbish, the whole of it! Nothing worth touching, and it is as dark as a
pocket up here, and cold, besides; how the wind blows in through
those knotholes! There's a mouse! If there is any thing that I hate, it's
mice! I'll tell you what it is, if old Peters thinks I'm going to stay up
here and tumble over his rusty nails, he's much mistaken. I wasn't
hired for that kind of work."

Whereupon John bounced down the attic stairs, three at a time, and
was found lounging in the show window, half an hour afterwards,
when Mr. Peters appeared.

"Have you put that box in order already?" was the gentleman's
question.

"I didn't find any thing to put in order; there was nothing in it but nails
and things."

"Exactly; it was the 'nails and things' that I wanted put in order; did
you do it?"

"No, sir, it was dark up there, and cold; and I didn't see any thing
worth doing; besides, I thought I was hired to run of errands."

"Oh," said Mr. Peters, "I thought you were hired to do as you were
told." But he smiled pleasantly enough, and at once gave John an
errand to do down town, and the boy went off chuckling, declaring to
himself that he knew how to manage the old fellow; all it needed was
a little standing up for your rights.

Precisely at six o'clock John was called and paid the sum promised
him for a day's work, and then, to his dismay, he was told that his
services would not be needed any more. He asked no questions;
indeed he had time for none, as Mr. Peters immediately closed the
door.

The next morning the old sign "Boy Wanted" appeared in its usual
place.